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  • Physics  (1,610)
  • 1980-1984  (1,610)
  • 1984  (555)
  • 1983  (538)
  • 1982  (517)
  • 1
    Unknown
    Amsterdam ; New York : North-Holland Pub. Co
    Keywords: DDC 530.1 ; LC QC20 ; Mathematical physics ; Physics ; Quantum theory ; Relativity (Physics)
    ISBN: 9780444875853
    Language: English
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  • 2
    Electronic Resource
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 241-244 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simplified approximation method for the treatment of dead-end and high conversion polymerization kinetics is presented. The method is based on the treatment of dead-end polymerization first described by Tobolsky. In appropriate circumstances, by contrast with Tobolsky's method, this method provides measurements of kd and kp/kt1/2 without recourse to the measurement of the monomer conversion at infinite time.Kinetic studies of free radical polymerizations are normally confined to measurements of initial rates. At low conversions the predictions of the general mechanism for chain-growth polymerization involving initiation, propagation, and termination steps are generally obeyed. Thus the polymerization rate should be first order in the vinyl monomer and half-order in the initiator concentrations.At high conversions, however, large deviations which can be ascribed to various effects can occur; for example, (1) the effect of the increasing viscosity of the polymerization medium on the termination rate constant kt, and possibly also on the propagation rate constant kp, which have been considered by North1 and Cardenas and O'Driscoll,2 or (2) depletion of the initiator as the polymerization progresses. This depletion will occur in all polymerizations but its significance will depend on the magnitude of the rate constant for initiator decomposition (kd) and the period of polymerization. Appropriate conditions will lead to limiting monomer conversion even after infinite polymerization time; this phenomenon has been called dead-end polymerization by Tobolsky.3Free radical polymerizations to high conversion are particularly important in the industrial context when initial kinetics are obviously inadequate. Suitable treatment of the conversion/time relationship is highly desirable.Senogles and Woolf4 have examined the polymerization of n-lauryl methacrylate at 60°C with 2-azobisisobutyronitrile as initiator under dead-end conditions.Here we propose a modification of Tobolsky's treatment of such polymerizations by using an approximation for the exponential decay in the initiator concentration. This method permits easy manipulation of the experimental data and the estimation of values for the kinetic parameters in favorable circumstances without recourse to the measurement of the conversion at infinite time or the evaluation of complicated functions of the monomer conversion. The method thus allows the duration of the laboratory experimentation to be significantly shortened and the complexity of the subsequent data analysis to be considerably reduced.
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  • 3
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 257-261 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 4
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 263-265 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 5
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 269-275 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel class of poly(metal phthalocyanino) benzimidazoles were prepared by the condensation reaction between metal (Cu, Co, and Zn), 4,4′,4″,4‴-tetracarboxyphthalocyanine, and 3,3′-diaminobenzidine. The reaction was investigated by melt and solution condensation methods. These polymers showed excellent thermal and thermooxidative stability and are noteworthy for their high char yield (86-90%) at 800°C in an anerobic atmosphere. Elemental analyses, spectra, and TGA studies were used to characterize these materials. Isothermal gravimetric analyses were carried out to determine their long-term thermal stability.
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  • 6
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 277-282 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ethyl acrylate (EA) and n-butyl methacrylate (n-BMA) copolymers were prepared in solution and the composition of the copolymer samples was estimated by 1H-NMR spectroscopic techniques. Because the characteristic signals, which vary with the composition of the copolymer, were absent, the ratio of intensities of down-field protons to that of the total protons was used for the estimation of copolymer composition. Reactivity ratios were calculated from these values by using the Kelen-Tudos differential linear equation.
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  • 7
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 299-310 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Amphiphilic block copolymers consisting of methacrylic acid (MA) sequences and p-N,N-dimethylaminostyrene (DMS) sequences were prepared by living anionic polymerization. DMS was polymerized by lithium naphthalene in tetrahydrofuran to yield a living polymer solution, to which trimethylsilyl methacrylate (TMSM) was added to allow the block copolymerization. The conversion of TMSM was dependent on the countercation, i.e., with Na+ as counterion, no quantitative conversion was reached owing to premature termination, whereas with Li+ the conversion was quantitative. The role of the counterion was discussed in some detail in connection with self-termination by the backbiting mechanism. The trimethylsilyl ester groups in the block copolymer were quantitatively hydrolyzed by treatment with aqueous methanol at room temperature, yielding MA sequences. The block copolymer of MA and DMS exhibited micellar properties in an aqueous solution.
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  • 8
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ten structurally different bisimide resins were prepared by reacting maleic anhydride/citraconic anhydride and benzophenone tetracarboxylic dianhydride with aromatic diamines and fused aromatic structures or heterocyclic groups. The amines included were 1,5-diaminonaphthalene, 2,5-bis(p-aminophenyl)1,3,4-oxadiazole, 3,3-bis(p-aminophenyl)phthalide, 9,9-bis(p-aminophenyl)fluorene. and 10,10-bis(p-aminophenyl)anthrone. These monomers were characterized by infrared (IR). 1H-NMR, mass spectroscopy, and elemental analysis. Thermal polymerization of these monomers was investigated by differential scanning calorimetry. Broad exothermic peaks were observed for a temperature range of 225-380°C. Temperature of exothermic peak position was influenced by the presence of substituents at the olefinic bond, and in biscitraconimides it was 40-50°C lower than in the corresponding bismaleimides. Anaerobic char yields of cured bisimide resins ranged from 44 to 64%. Oxadiazole-containing bisimides had low thermal stability. Increase in formula weight between the imide groups did not influence the char yields in a systematic manner. Graphite cloth laminates with two of these bisimide resins were fabricated and tested for a number of physical properties. Their limiting oxygen index was 70-72%.
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  • 9
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2765-2772 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Charge transfer (CT) interaction is described in semiconducting dispersions of TCNQ complex salt \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm Et}_3 {\rm NH}^+ ({\rm TCNQ})_2^{\cdot^{\hskip-3.7pt\hbox{--}}}$\end{document} with and without added TCNQ°, in poly(vinyl acetal) matrices in which the electron-donor moiety is varied. The extent of CT interaction was determined in films and in solution (DMF, acetonitrile, or methylene chloride) through the absorbances at 398 nm (\documentclass{article}\pagestyle{empty}\begin{document}$ {\rm TCNQ}{\ }^{\cdot^{\hskip-3.7pt\hbox{--}}}$\end{document} and TCNQ°) and 857 nm \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm TCNQ}{\ }^{\cdot^{\hskip-3.7pt\hbox{--}}}$\end{document}. Resistivity of the conductive films was related to the stoichiometry of TCNQ species in the films and found to have a minimum at \documentclass{article}\pagestyle{empty}\begin{document}$[{\rm TCNQ}^\circ]/[{\rm TCNQ}{\ }^{\cdot^{\hskip-3.7pt\hbox{--}}}]\simeq 1$\end{document}. Lower resistivities were attained with films having a uniform, densely packed dispersion of microcrystallites which were obtained at a relatively slow solvent removal rate. With this particular complex salt, strong electron-donor polymers are found to be better matrices for semiconductivity.
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  • 10
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2773-2780 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(metal phthalocyanine)imides of copper, cobalt, nickel, and zinc were synthesized by the reaction of metal phthalocyanino tetramines with benzophenone tetracarboxylic dianhydride. These polymers were characterized by elemental analyses and IR, TGA, and inherent viscosity studies. Noteworthy features of these phthalocyanine polymers are their remarkable thermal and thermooxidative stabilities with char yields at 800°C that range from 78 to 83% in a nitrogen atmosphere. The relative thermal stabilities of these polymers have been evaluated by activation energy measurements.
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  • 11
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2781-2789 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New poly(metal phthalocyanine) pyromellitimides of copper, cobalt, nickel, and zinc were synthesized and elemental, IR, TGA, and inherent viscosity measurement studies were done to characterize these polymers. They showed exceptional thermal and thermo-oxidative stability with char yields at 800°C ranging from 75 to 87% in a nitrogen atmosphere. The ratio of the polymer decomposition temperatures in air and nitrogen (PDT) (air)/PDT (N2) varied from 0.91 to 0.97, which indicated that the onset of degradation of these polymers is greatly affected by the presence of an oxidizing atmosphere. Isothermal studies were done to evaluate the long-term thermal stability of these polymers.
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  • 12
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alternating copolyamides of various ω-amino acids were synthesized by base-catalyzed polycondensation of N-isothiocyanatoacyl ω-amino acids in solution. Derivatives of the following amino acids were used: glycine, β-alanine, γ-aminobutyric acid, δ-aminovaleric acid, ε-aminocaproic acid, D,L-β-aminobutyric acid, trans-4-aminocyclohexane 1-carboxylic acid, 4-aminophenyl acetic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 3-amino-4-methyl benzoic acid, and 4-amino-3-methyl benzoic acid. The base-catalyzed polycondensation at lower temperatures gave purer products than the bulk condensation at 180-200°C. 13C-NMR and natural-abundance 15N-NMR spectra measured in trifluoroacetic acid demonstrate that in most cases undisturbed alternating sequences were obtained. Strong neighboring residue effects and long-range sequence effects were found in the 15N-NMR spectra, and structure/shift relationships are discussed. The sequences of copolyamides obtained by copolymerizations of lactams or β-amino acid N-carboxyanhydrides were investigated by both 15N-NMR and 13C-NMR spectroscopy. 13C-NMR spectroscopy was found to be more useful if the copolyamides consist of ω-amino acid units of different chain length. However, 15N-NMR spectroscopy is more suited if the monomer units differ exclusively by their substituents.
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  • 13
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2809-2817 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This article concerns the synthesis and characterization of new epoxy and aldehyde telechelic polyisobutylenes, that is, and . The synthesis of the epoxy derivative was achieved by quantitative epoxidation of α,ω-di(isobutenyl) polyisobutylene with m-chloroperoxybenzoic acid and that of the dialdehyde by quantitative isomerization of the epoxy termini with zinc bromide. Infrared (IR) and 1H-NMR analysis of these new telechelic polymers and ultraviolet (UV) analysis of the 2,4-dinitrophenylhydrazine derivative of the dialdehyde indicate quantitative conversions and yields, that is, essentially theoretical functionalization (Fn = 1.95 ± 0.05).
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  • 14
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2819-2828 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of α-methylene-γ-butyrolactone (α-MBL) homopolymerization was investigated in N,N-dimethylformamide (DMF) with azobis(isobutyronitrile) as initiator. The rate of polymerization (Rp) was expresed by Rp = k[AIBN]0.54[α-MBL]1.1 and the overall activation energy was calculated as 76.1 kJ/mol. Kinetic constants for α-MBL polymerization were obtained as follows: kp/kt1/2 = 0.161 L1/2 mol-1/2·s-1/2; 2fkd = 2.18 × 10-5 s-1. The relative reactivity ratios of α-MBL(M2) copolymerization with styrene (r1 = 0.14, r2 = 0.87) were obtained. Applying the Q-e scheme led to Q = 2.2 and e = 0.65. These Q and e values for α-MBL are higher than those for MMA
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  • 15
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2829-2838 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of methacryloyl fluoride (MAF) homopolymerization was investigated in methyl ethyl ketone (MEK) with azobis(isobutyronitrile) as initiator. The rate of polymerization (Rp) followed the expression Rp = k[AIBN]0.55[MAF]1.18. The overall activation energy was calculated as 74.4 kJ/mol. The relative reactivity ratios of MAF(M2) copolymerization with styrene (r1 = 0.083, r2 = 0.14), and methyl methacrylate (r1 = 0.48, r2 = 0.81) in methyl ethyl ketone were obtained. Application of the Q-e scheme (in styrene copolymerization) led to Q = 2.22 and e = 1.31. The glass transition temperature (Tg) of poly(MAF) was 90°C by thermomechanical analysis. Thermogravimetry of poly(MAF) showed a 10% weight loss of 228°C in air.
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  • 16
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2851-2862 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of acetylene-terminated quinoxaline oligomers was synthesized for testing as possible adhesives for airplane manufacturing.
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  • 17
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 529-539 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolymerization of N-carboxy N∊-carbobenzoxy L-lysine anydride with N-carboxy β-benzyl L-aspartate anhydride was initiated with n-butylamine in acetonitrile. The copolymerization proceeded almost homogeneously except for the initial stage, when the proportion of N-carboxy anhydride (NCA) in the polymerization mixture varied from 25 to 75 mol %. This was due to the fact that the copolypeptides formed were soluble or highly swollen in the solvent, in contrast to the homopolymerization of NCAs such as N∊-carbobenzoxy L-lysine NCA and β-benzyl L-aspartate NCA in acetonitrile, which proceeds heterogeneously. The compositions of the copolymers obtained were, within experimental error, the same as their monomer feed compositions. The initial rates of copolymerization were almost the same as the rate of homopolymerization of β-benzyl L-aspartate NCA, which propagates with a nonhelical polypeptide, but were slower than the rate of homopolymerization of N∊-carbobenzoxy L-lysine NCA, which propagates with a helical polypeptide.
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  • 18
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 555-563 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Effect of polyanions on the aggregation of methylene blue (MB) was investigated spectrophotometrically. The following polyanions were used: potassium poly(vinyl sulfate), potassium poly(styrenesulfonate), sodium poly(methacrylate), and sodium poly(acrylate). The state of aggregation was largely dependent on the kind of polyanion and polyanion-MB ratio. MB-photo-sensitized isomerization of cis-p-(phenylazo)phenyltrimethylammonium iodide(cis-PTA) to the transisomer was used advantageously to investigate the effect of dye aggregation on the triplet excitation energy transfer between cationic dyes bound to polyanions. Although the efficiency of the excitation energy transfer between MB and cis-PTA was enhanced by the addition of polyanions, the formation of highly aggregated MB reduced the efficiency of the excitation energy transfer. Correlation with the dye aggregation induced by polyanions and the efficiency of excitation energy transfer between dyes was discussed.
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  • 19
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 663-673 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polybenzimidazoles that contained anthracene photodimer were prepared. The molecular weights of the polymers prepared by the photopolymerization of bis-anthrylbenzimidazoles were limited by the precipitation of the resulting polymers from the reaction organic solvents. Higher molecular weight polymers were obtained by the photopolymerization of bis-anthryl-Schiff's bases, followed by the oxidation of the resulting polymers. These polymers were soluble in acidic solvents such as formic and sulfuric acids but were insoluble in organic solvents.
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  • 20
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 675-681 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of methyl methacrylate in the presence of a mixed ligand complex, [N,N′-ethylenebis(salicylideneiminato)](acetylacetonato)cobalt(III) in benzene was studied. The rate of polymerization was proportional to the square root of the concentration of the chelate and the monomer exponent was 1.67 and 1.69 at 60 and 70°C, respectively. The activation energy and the kinetic and transfer constants were evaluated. A free-radical mechanism has been proposed.
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  • 21
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 707-724 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetic behavior of a Cr6+/Cu2+ system in its reaction with wood has been elucidated. The same reactions with carbohydrates and lignin of wood for CrVI alone are still present. Approximately 20% of the copper is fixed to the guaiacyl units of lignin in the form of copper chromate; the remaining copper forms complexes with cellulose and mainly with the guaiacyl units of lignin. The CrVI/lignin guaiacyl unit complexes already found for the treatment of wood with CrO3 are still the main CrVI complexes formed. Copper chromate is present as [Cu(H2O)2(guaiacol)]CrO4(guaiacol) complexes, and CuCrO4 bridges between different guaiacyl units of the lignin network appear to be likely. Substantial interference of the Cu2+ ions in the second-zone reactions of CrVI with wood occurs. The amount of CrVI and CrIII fixed onto lignin and cellulose compares well with experimental values. Rate constants, energies of activation, and Arrhenius equations of the various reactions have been obtained. The amount of Cu2+ interference in the reaction has also been calculated.
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  • 22
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 683-689 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Random polyamide-esters were prepared directly by the interfacial and solution polycondensation of 4-(4-amino-α,α-dimethylbenzyl)phenol (I) with iso- and terephthaloyl chlorides. Authentic samples of ordered polyamide-esters with an amide-amide-ester-ester structure were synthesized by the two-step procedure; that is, the preparation of amide-bisphenol monomers from I and subsequent polycondensation with aromatic diacyl chlorides. The random and ordered polyamide-esters differed from one another with respect to solubility in organic solvents and glass transition temperature, whereas all the random and ordered polymers were of equal low crystallinity. All of these polymers began to decompose around 350°C in both air and nitrogen atmospheres.
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  • 23
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 691-706 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Perfluoro-2-butyl tetrahydrofuran was polymerized by an RF glow discharge technique and detailed ESCA studies were made of the resultant films. The rate of film deposition was sensitively dependent on the W/FM parameter and the site of deposition. The ESCA data show that the molecular rearrangement accompanying plasma polymerization and the oxygen functionality is at a significantly lower level than the starting material. Under appropriate conditions plasma polymerization produces material with a C:F stoichiometry of 1:2, although the ESCA data show that the polymer is drastically different from PTFE. ESCA studies are also reported on thin films of the monomer studied at low temperature.
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  • 24
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 725-738 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetic behavior of a Cr/As system in its reaction with wood is described, as are its reactions with lignin and carbohydrates of wood for CrVI alone. ChromiumIII arsenate complexes with the guaiacyl units of lignin, as well as the usual chromic acid/guaiacyl unit complexes already characterized, was formed. The interference of As concentration on the various zones of fixation of chromium are identified. Complexes between guaiacol and chromium arsenates indicate that in this Cr/As system CrIII can also be linked to the guaiacyl units of lignin when in the form of CrAsO4·6H2O contrary to what obtained with systems not containing As. An initial increase in the rate of reduction CrVI → CrIII by the carbohydrates fraction in wood is ascribed to the catalytic effect of the arsenic. The percentages of chromium fixed onto lignin and cellulose of wood compare well with experimental values.
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  • 25
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 765-774 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complex dielectric constants were measured at frequencies of 0.1-10,000 kc/s over the temperature range of 0-60°C in medicated cotton cellulose and viscose. In these fibers evidence is found for a new secondary relaxation process within the frequency region of 0.1-1 kc/s. The significance of the results is discussed.
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  • 26
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3107-3114 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyethylene films were evaporated in gas plasmas of Ar, N2, O2, and H2O. The deposits were analyzed by infrared (IR) spectroscopy to determine the concentration of characteristic functional groups. The deposit prepared in Ar-atmosphere had a rather high concentration of methyl group and many double bonds were produced in the film. The deposits prepared in Ar- and N2-plasmas produced similar spectra, which showed twice the concentration of methyl group than the deposit in Ar-atmosphere and also contained a few carbonyl and hydroxyl groups. The film treated in O2-plasma contained the largest amount of carbonyl group and the lowest number of double bonds among the plasma-treated deposits. Dielectric loss curves against temperature for the deposits treated in these plasmas showed a broad peak near 20°C. For O2-plasma-treated film the loss tangent curves showed a sharp maximum. The activation energy for the relaxation of Ar-, O2-, and H2O-plasma-treated films had the same value of 50.6 kcal/mol. The observed relaxation in the films prepared in gas plasmas was considered due to the β process and was attributed to the motion of oxidized branched polyethylene.
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  • 27
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 775-782 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Spin-lattice relaxation times and nuclear Overhauser enhancements (NOE) for 13C nuclei in copolymers of acrylonitrile and vinylidene chloride were measured at 20.1 and 67.9 MHz. In the —CCl2— region of the spectrum T1 and NOE values of the various resonances are equal within experimental error and are invariant to changes in composition. The T1 and NOE values of the —CCl2— region, however, are not equal to those of the —CH— or —CN region. As a result compositions cannot be calculated by direct comparison of the areas in the —CCl2— region and either the —CH— or the —CN region. Discrepancies can be corrected for the —CH— resonances by multiplication of the area by an empirical constant. A similar constant for the —CN region is composition-dependent at 20.1 and 67.9 MHz. A chemical shift anisotropy mechanism is postulated as important for relaxation of the —CN resonances. The overall influence of variable T1 and NOE values on quantitative determination of polymer composition is considered.
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  • 28
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 783-793 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It was found that 1-substituted quaternary imidazolium compounds show some characteristic infrared (IR) activity. On quarternization of 1-substituted imidazoles strong absorption bands appeared at about 1150 and 1550 cm-1 in the IR spectra of these compounds. The band at 1150 cm-1 was assigned to the position 2 C-H bending mode and the 1550 cm-1 band was attributed to a ring vibration mode of the quaternary imidazolium compounds. The concentration of the quaternary imidazolium units in a polymer can be determined by measuring the intensity of the absorption bands at 1150 or 1550 cm-1 in relation to another suitable absorption band of the spectrum.
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  • 29
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3147-3154 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The star-branched polymers on the tetrahedral lattice are studied by means of the Monte Carlo method. The influence of solvent quality on the dimensions of the coil is described for both linear and branched polymer systems of different functionality. It has been observed that the ratios of gyration radii 〈S2〉b/〈S2〉l are greater than those predicted theoretically for the random-flight model. The fourth reduced moment of S2 distribution and the mean-square separation of the branch ends from the center of gravity have been also computed. The changes in segment arrangement in the coil with increasing number of branches have been observed.
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  • 30
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 795-810 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isothermal emulsion polymerization at 60°C of styrene in a batch reactor were studied by using sodium lauryl sulfate as surfactant and potassium persulfate as initiator source. The concentrations of surfactant and initiator were varied during the runs. The polymerization evolution was followed as samples were taken at regular intervals. These emulsion samples were analyzed for monomer conversion, rate of polymerization, as well as for the size and the size distribution of the particles. The molecular weight and molecular weight distribution were obtained by gel permeation chromatography. Our study showed that fresh nucleation takes place even at high conversion, causing a continuous shifting toward broadening of particle size distribution. Contrary to the theory of Smith and Ewart, which assumes a constant number of particles during interval II of the polymerization reaction, our digital simulation of the reaction presents better experimental results with a variable number of particles, and indicates that the Hui-Hamielec model for termination constant kt as function of conversion is not applicable under our working conditions.
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  • 31
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 817-838 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Random copolymers of acrylamide with sodium-2-sulfoethyl methacrylate and with sodium-2-acrylamido-2-methylpropane sulfonate were synthesized in aqueous solutions utilizing persulfate initiators. Copolymer compositions were determined by elemental analysis and by infrared spectroscopic methods. Monomer reactivity ratios were calculated using Fineman-Ross, Kelen-Tüdos, and/or Mayo-Lewis techniques at appropriate conversions. The copolymer microstructure, including mean sequence length distributions, was calculated from reactivity ratios. Membrane osmometry and viscometry measurements were utilized to estimate molecular weight and size. The large dimensions of these polyelectrolytes in aqueous solutions, as well as their inherent hydrogen bonding capacity and pseudoplasticity, make these copolymers excellent candidates for application as mobility control agents in enhanced oil recovery.
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  • 32
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 839-846 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyiodide formed by complexation of poly(vinyl acetate) (PVAc) with iodine in the presence of iodide has been investigated by chemical analysis and resonance Raman spectrophotometry. When PVAc films were immersed in iodide-iodine aqueous solutions which had different ratios of iodide to iodine concentration [I-]/[I2], the complex films exhibited tremendous variations of swelling degree, despite the relatively small change in the amount of bound iodine. From a quantitative chemical analysis, the composition of polyiodide bound to PVAc was found to be 1.01 ± 0.035 in the molar ratio of iodide to iodine irrespective of the composition of the iodide-iodine aqueous solution ([I-]/[I2] = 2-500). The polyiodide formed in PVAc-iodine-iodide complex was therefore inferred to be (I3-)n. Resonance Raman spectra obtained on PVAc-iodine-iodide complexes were also identical to those of the benzamide-iodine complex, in which the polyiodide consists of (I3-)n, consistent with the result from chemical analysis.
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  • 33
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3189-3197 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of poly(vinyl chloride) powder with aqueous sodium hydroxide solution in the presence of quaternary ammonium or phosphonium halides yielded dehydrochlorinated products of conjugated polyene structure. The reaction was discussed in terms of a phase transfer catalytic mechanism between aqueous and polymer phases. Among the catalysts used tetrabutylammonium bromide was the best. To obtain the optimum conditions the effects of reaction temperature, the concentration of NaOH and the catalyst, and the molecular weight of poly(vinyl chloride) were investigated. Treatment of PVC films and solutions in tetrahydrofuran with aqueous NaOH solutions under two-phase conditions also produced dehydrochlorinated films and powders.
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  • 34
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3199-3205 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Lithium-metallated (styrene-p-benzylstyrene)copolymer was reacted with chlorine-terminated polystyrene as a crosslinker polymer in a mixture of tetrahydrofuran (THF)-n-hexane at 25°C in the presence of lithium chloride(LiCl). The rate constants were estimated from the changes in the concentration of metallated polymer by photometrical measurements. As a result, the rate constant of grafting (k1) showed a constant value in spite of a change in molecular weight of the crosslinker polymers and the addition of n-hexane. The rate constant of intramolecular crosslinkings (k2intra) obtained in a mixed solvent (21 ∼ 36 vol % of n-hexane) increased when the molecular weight of the crosslinker polymers and the extent of n-hexane were increased.
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  • 35
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3207-3217 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical cyclopolymerization of allyl methacrylate (AMA) was investigated in detail, especially under the specified conditions; that is, above the ceiling temperature for a head-to-tail propagation (ΔGht ≥ 0) in the polymerization of methacrylate. Thus the structure of the polymer obtained was examined by 1H- and 13C-NMR and infrared (IR) spectroscopy; no existence of unreacted pendant methacrylyl groups was observed, which suggests that, as a cyclopolymerization mechanism of AMA, intermolecular propagation of growing radicals, followed by intramolecular cyclization or intermolecular propagation of the resulting uncyclized methacrylyl radical, occurs exclusively with methacrylyl group. Temperature dependency of cyclization constant Kc was unusual; Kc increased rapidly at elevated temperatures and no linear relationship of ln Kc vs. 1/T was observed. Five-membered ring formation was favored at an elevated temperature and diluted monomer concentration. These results are discussed thermodynamically in terms of controlled ring closure in cyclopolymerization.
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  • 36
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    Notes: β-Pinene was polymerized with H2O/BCl3 (protic) and p-dicumyl chloride and sym-tricumyl chloride (nonprotic) inifer systems in CH2Cl2 or CH2Cl2/n-C6H14 solvents from -10 to -70°C. The effect of solvent polarity, temperature, and monomer and inifer concentration on conversions and molecular weights was investigated. Low conversions and molecular weights, M̄n = 1300-2500, obtained under these conditions suggest rapid termination.
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  • 37
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 901-915 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The anionic polymerization of 1.3-cyclohexadiene (1.3-CHD) was investigated in temperatures that ranged from 25 to -77°C. Initiation by lithium naphthalene (N-·,Li+) in tetrahydrofuran at -20°C yields polymers with fairly narrow molecular weight distribution. The M̄w of these polymers so prepared is ca. 20,000. Polymerization of 1.3-CHD conducted at room temperature is accompanied by the dehydrogenation and disproportionation of the monomer, especially when N-·,K+ acts as initiator. Oligomers are formed when hexamethylphosphoramide is used as a solvent. The mechanism of the initiation of the polymerization of 1.3-CHD by N-·,Li+ was elucidated and the rate constants at -20°C in tetrahydrofuran of the elementary reactions were determined. It was established that the dianions formed by disproportionation of N-·,Li+ act as effective initiators for 1.3-CHD. The adducts formed constitute the cyclohexanyl and naphthyl carbanionic groups. The former carbanions (λmax ∼ 275 nm) propagate the polymerization. The initially formed dimeric adducts are stabilized by the separation of the carbanionic end groups by the additional monomer units. Chain transfer to the monomer limits the growth of the polymers. The isomerization of the cyclohexadienyl anions, formed as result of chain transfer, may be followed by the elimination of lithium hydride. The latter reaction represents a termination step. Addition of 1.4-CHD to the reaction mixture enhances the chain transfer and the termination.
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  • 38
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 929-938 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies of the effect of aqueous Br2 solution on the fine structure of cellulose have shown that the accessibility of the cellulose is a complex function of the duration of treatment. Following immersion of rayon-cellulose in the Br2 solution, its accessibility is observed to increase until a peak is reached, after which the accessibility decreases with time. For higher temperatures and greater concentrations of Br2, a sharper peak and faster rates of increase and decrease of accessibility are obtained. In order to explain this behavior, a mathematical model of the kinetics is postulated involving two opposing first-order processes occurring simultaneously. One process describes the decrystallization of crystalline regions within the cellulose by opening intermediate linkages due to Van-der-Waals forces involved. The second process relates to the crystallization of the less-ordered regions. The rate constants for these processes are determined by fitting experimental curves to the postulated analytical expression with the aid of a digital computer program. Experiments carried out on high-modulus rayon showed that for this type of cellulose, the effect described above was very pronounced. From the calculated rate constants, the activation energies of the crystallization and decrystallization reactions were determined. The plots of the rate constants versus 1/T showed that a break occurs at 25°C, corresponding to a second-order transition point of cellulose. The energies of activation of the crystallization process are in the range of 7-9 and 10-13 kcal/mol in the temperature ranges 10-25 and 25-40°C, respectively. The activation energies of the decrystallization process are 13 and 18-24 kcal/mol in these temperature ranges.
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  • 39
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3265-3265 
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    Keywords: Physics ; Polymer and Materials Science
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  • 40
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3267-3270 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the basic hydrolysis of several poly(phenyl methacrylates) with different substituents in the aromatic ring were investigated. Using Keller's equations to describe the effect of neighboring groups on the kinetics of side-group reactions in polymers, we computed the corresponding rate constants which correlated well with Hammett's substituent constants.
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  • 41
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    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.
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  • 42
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3285-3296 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C-NMR spectra of bulk acrylonitrile-butadiene-styrene (ABS) resin are reported. The styrene-co-acrylonitrile (SAN) carbons can be observed selectively by using high-power proton decoupling, cross polarization, and magic angle spinning (MAS). The polybutadiene (PBd) carbons can be observed selectively by using low-power proton decoupling, with or without MAS. Methods and conditions for using 13C-NMR to quantify the amount of PBd in solid ABS resins are developed. The 13C-NMR results and results from iodine monochloride titrations for PBd content are in good agreement. Resonances of PBd in ABS in the solid state are assigned on the basis of triad sequences of cis, trans, and vinyl-1,2 geometric isomers of butadiene. Computational methods are set forth for measuring directly from the 13C-NMR spectra the percent of cis, trans, and vinyl-1,2 isomers in PBd in the ABS resin. The NMR measurement of PBd microstructure appears to be preferable to infrared (IR) determinations. Relaxation parameters (T1 and NOE) are reported for PBd in bulk ABS as a function of temperature and are analyzed in terms of a distribution of rotational correlation times. These relaxation parameters are similar to those of nongrafted PBd and indicate that the local motions in grafted and nongrafted PBd are similar.
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  • 43
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3305-3312 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The second moments of the ESR signals obtained from poly(p-phenylene) (PPP) and deuterated PPP were measured at 9.5 and 35 GHz. The theoretical and experimental contributions to the second moments were considered. It is shown that for deuterated PPP, deuteron hyperfine splitting makes a negligible contribution to the observed second moment. The proton hyperfine contributions to the second moments of the radical species in PPP and p-sexiphenyl were estimated and it was concluded that the unpaired electron was delocalized over only 2-4 phenylene units. A rationale is offered in terms of polarons present as defects in the PPP chains.
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  • 44
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1011-1019 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The characteristics of the photoinduced electron transfer reaction from polystyrene pendant tris(2,2′-bipyridyl)ruthenium (II) complex [Ru(bpy)32+] to methylviologen (MV2+) were studied. The rate constant k1 from the excited state of the complex, Ru(bpy)32+*, to MV2+ were determined for both the polymeric and monomeric complexes from the lifetime τ of Ru(bpy)32+* and the quenching rate of Ru(bpy)32+* by MV2+. The polymer pendant Ru(bpy)32+* showed three kinds of τ components ranging from 7 to 474 ns, in contrast to the monomeric complex, which showed one component of 350 ns. The k1 values for both complexes were almost the same, on the order of 108 L/mol s. The photoinduced electron transfer from solid-phase Ru(bpy)32+ to liquid-phase MV2+ was realized by utilizing the polymer complex, and the solid-liquid interphase reaction system is discussed.
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  • 45
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3337-3350 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It was found that structurally isomeric polymers were formed by the ring-opening polymerization of β-(2-acetoxy ethyl)-β-propiolactone with (EtAlO)n and Et(ZnO)2ZnEt catalysts; that is, the Al catalyst catalyzed normal polymerization which led to poly-β-ester and the Zn catalyst formed isomerized poly-β-ester as the main product. The polymer structure was determined by nuclear magnetic resonance (NMR), T1-value, thermal decomposition product, and (Tg). The NMR studies for the monomer-catalyst systems indicated that the Al catalyst interacted predominately with the lactone group, whereas the Zn catalyst interacted with the side-chain ester group. These site-selective interactions could be related to the difference in the stereoregulation by the two catalysts during the poly(β-ester)-forming polymerization process.
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  • 46
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3351-3368 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polydimethylsiloxane oligomers with silanol ends condense in aqueous dispersion under mild conditions to form high polymers in the presence of sulfonic acid surfactants. The process follows a second-order rate law in silanol if reversibility is taken into account. The second-order rate constant is proportional to the area at the oil-water interface and is a complex function of surfactant concentration. The principal driving force is the heat of condensation of the water produced in the polymerization. A mechanism paralleling surface catalysis is offered in which a termolecular complex that consists of two surfactant molecules and one silanol end group reacts bimolecularly at the oil-water interface.
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  • 47
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3369-3376 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This article deals with the kinetics and mechanism of acrylonitrile (AN) polymerization initiated by Cu(II)-4-anilino 3-pentene 2-one[Cu(II)ANIPO], Cu(II)-4-p-toluedeno 3-pentene 2-one [Cu(II)TPO], and Cu(II)-4-p-nitroanilino 3-pentene 2-one [Cu(II)NAPO] in bulk at 60°C. The polymerization is free radical in nature. The exponent of initiator(I) is ≃ 0.5. The initiation step is a complex formation between the chelate and monomer and subsequent decomposition of the intermediate complex giving rise to free radical and Cu(I). This is substantiated by ultraviolet (UV) and electron spin resonance (ESR) studies. The activation energies and kinetic and chain transfer constants have also been evaluated.
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  • 48
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3377-3385 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cationic copolymerization of tetrahydrofuran-(A)-3,3-dimethyloxetane (B) was studied at 0°C with BF3·OEt2-epichlorhydrin and acetylhexafluoroantimonate as initiators. The values of the reactivity ratios, calculated by the Fineman-Ross and Kelen-Tüdos methods, were rA = 0.13, rB = 8.1 and rA = 0.13, rB = 7.9, respectively. These values are in satisfactory agreement with those obtained with a kinetic scheme in which depropagation reactions were considered. The product rArB was approximately equal to unity, which indicated an ideal random copolymerization. The copolymers were also analyzed by 1H-NMR spectroscopy. Their spectra presented a doublet at 3.1 and 3.15 ppm that corresponded to the methylene protons of the dimethyloxetane units and allowed the determination of the probabilities P(AA), P(AB), and P(BB). Good agreement was found between the values calculated by spectroscopic methods and those obtained by using the classical probability theory of copolymerization.
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  • 49
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3387-3397 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel class of polyamide-quinazolinediones was synthesized by the polymerization of 2,2′-disubstituted bis(1,3,4-oxadiazolin-5-ones) with aromatic bis-o-amino esters in m-cresol. The polymerization probably proceeded in the formation of ring-opening adducts, which in turn were cyclized by the elimination of alcohol to give polyamide-quinazolinediones. These polymers, which were soluble in polar aprotic solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide, had, with one exception, reduced viscosities in the range of 0.12-0.32 dL/g. Thermogravimetric analyses indicated that they began to decompose at 310-360°C in air.
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  • 50
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3421-3429 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of reaction of 1-halooctanes with aqueous sodium cyanide catalyzed by phosphonium salts attached to insoluble polystyrene resins by tetramethylene or heptamethylene spacers was studied as a function of catalyst particle size, degree of polymer crosslinking, percentage of ring substitution, and temperature. Rates of reaction of 1-bromooctane with 17-38% ring-substituted catalysts increased as spacer-chain length increased. Rates of reaction of 1-bromooctane decreased, whether the percentage of ring substitution increased or decreased from 17-19%. Rates of reaction of 1-chlorooctane increased with increasing spacer-chain length and decreasing percentage of ring substitution. Apparent activation energy for the reaction of 1-bromooctane with 9% ring-substituted, spacer-modified catalysts was 9-10 kcal/mol and 13 kcal/mol with 17-19% ring-substituted catalysts. The hydrophilicity of catalysts decreased with increasing spacer-chain length and decreasing percentage of ring substitution. The mechanisms of reaction were discussed in terms of intrinsic reactivity and intraparticle diffusion limitations on the reaction rates.
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  • 51
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3447-3450 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 52
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    Topics: Chemistry and Pharmacology
    Notes: A series of oligomer model compounds of polyethyleneimine derivatives with pendant adenine bases were prepared by the reaction of a carboxyethyl derivative of adenine with oligomeric amines, using an activated ester method. To evaluate the intramolecular interaction between pendant adenine bases in these compounds, ultraviolet spectra at various pH regions were measured. Ultraviolet hypochromicities and pKa values depended linearly on the chain length of the oligomers. The results showed that the intramolecular interactions of adenine bases were realized less in their protonated than neutral forms.
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    Topics: Chemistry and Pharmacology
    Notes: A versatile and high-yielding method was developed for specifically modifying galactose-containing polysaccharides, exemplified here by two representative galactomannans, guar gum 1 and locust bean gum 5. Oxidation of the primary alcohol functions of 1 and 5 with galactose oxidase produced the corresponding aldehyde derivatives 2 and 6 which were subsequently derivatized in several ways. Reductive amination with sodium cyanoborohydride of 2 and 6 proceeded smoothly (60-90% yields) and led to stable amine derivatives (4, 7-11), which included hydroxyalkylamine- (8), glycine- (9), and BSA- (11) derivatives. The cationic primary amine derivative 12 was similarly reductively alkylated with lactose to yield a product 13 with extended carbohydrate side chains. Oxidation of 2 produced the anionic carboxy derivative 14, whereas reduction of 2 and 6 with sodium borodeuteride yielded the deuterium labeled neutral species 15 and 16. The undegraded gums and some of their derivatives were studied by high resolution 13C-NMR (100.6 MHz) at 30°C, and the proposed chemical shift assignments were in good qualitative agreement with those of earlier studies. ESR spectroscopy was used to follow the chemical reactions and to derive information about the galactose distribution of 1 and 5. Mean nearest neighbor distances (r̄) between nitroxides attached to 1 and 5 were 1.36 nm (±5%) for 4 and 1.75 nm (±5%) for 7. These r̄ values agree favorably with the structural models recently proposed elsewhere, excluding earlier suggestions of homogeneous galactose distributions or regularly alternating blocks of branched and unbranched mannose units. The solution properties, such as viscosity and salt- and organic solvent-compatibility, of some of the guar derivatives appear to be unique and interesting. An alternative oxidation procedure of the galactose residues of 1 and 5 with sodium periodate has been evaluated.
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  • 54
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1279-1285 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymerization of β-pinene with styrene oxide (SO) and β-pinene with N-vinylpyrrolidone (VP) was investigated by using SnCl4 in dichloromethane diluent at low temperature. Monomer reactivity ratios were evaluated for both copolymers at -80°C; these are r1(SO) = 2.979 and r2(β-pinene) = 0.002 and r1(VP) = 0.096 and r2(β-pinene) = 0.294.
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  • 55
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1287-1298 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Five polyimide films prepared from 3,3′,4,4′-benzophenone tetracarboxylic acid'dianhydride (BTDA) and diamines, 4,4′-oxydianiline (ODA), 3,3′-diaminobenzophenone (DABP), or 3,3′-diaminodiphenylcarbinol (DADPC) and doped with Li2PdCl4 (LTP) or Pd[(CH3)2S]2Cl2 (PDS) were selected for a detailed x-ray photoelectron spectroscopic (XPS) study to determine the oxidation state of palladium and the relative distribution of this and other elements in these films, especially as they relate to electrical resistivity. XPS shows that Pd in the films is present as a mixture of zero and +2 valence states. Films that contain lithium as part of the dopant all show that metal is present as Li+ and Li2O, a fact that may have a bearing on film electrical properties. An Auger electron spectroscopic (AES) or XPS profiling was performed on two of the electrically conductive films. A film doped with PDS reveals a majority of palladium at the surface as Pd(0) and much smaller amounts in film bulk as a mixture of Pd(0) and Pd(II). Film behavior is similar to a metal-vapor deposited film. An LTP doped film, by contrast, exhibits a homogeneous composition with a mixture of Pd(0) and Pd(II). These studies support others that use chemical etching on the film surfaces. Scanning electron microscopy (SEM) has been used to provide surface evaluations.
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  • 56
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1299-1313 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is well known that the reaction rate and molecular weight of vinyl polymers can change markedly during the course of polymerization and that these changes are due to the influence of diffusion on the termination reaction. The chain length dependence of the termination rate constant has been considered in this work and has resulted in a general method of treating the polymerization kinetics and molecular weight distribution. This method is independent of the form of the chain length dependency and is capable of dealing with both disproportionation and recombination modes of termination. A specific model for the termination rate constant with chain length dependence is proposed and is based on free volume theory and entanglement coupling. Master curves for the characteristics of the reaction rate and molecular weight distribution are presented with the application of this model.
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  • 57
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1315-1329 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is frequently observed that the gel effect in vinyl polymerizations decreases in intensity at about the 50-70% conversion level. This is apparent in both rate and molecular weight data. It is postulated that there should be a limitation on the decrease in the termination rate constant to explain this effect. As an extension of the general theory of chain length dependent termination behavior, a general treatment of the gel effect with a limiting value of the termination rate constant is presented. A specific model is proposed for this limited rate constant which is based on the simple consideration that as translational movement of macroradicals becomes increasingly difficult the contributions made by segmental motion derived solely from the propagation reaction will be the prevailing mechanism. The termination reaction changes from chain length dependent to chain length independent during this transition period.
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  • 58
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1331-1344 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The values of the parameters that are necessary to compute the free volume changes accompanying polymerization were determined from viscosity data of concentrated polymer solutions. Relationships applicable above and below the glass transition temperature of the polymer were quantified. A general treatment of the variation of the propagation rate constant with free volume was postulated, based on the variation of the monomeric diffusivity with free volume. This, in turn, was related to the friction coefficient of a polymer chain segment, the values of which are readily available. A discussion of the reaction behavior in the last stage of polymerization and the occurrence of limiting conversion is also presented.
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  • 59
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1345-1371 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bulk polymerization data of methyl methacrylate, ethyl methacrylate, ethyl acrylate, n-propyl acrylate, vinyl acetate, and styrene were compared with the predictions of the theory proposed in the earlier parts of this series (I-III). This theory of polymerization kinetics uses the concepts of free volume and chain entanglements to describe the relationship between chain mobility and chain length dependent termination reactions. Excellent agreement was found between the predictions of the theory and the polymerization rate and molecular weight data of the six polymerization systems studied. Emphasis was placed on the ability to explain the development of higher order molecular weight averages (M̄w, M̄z, etc.) because they provide the most crucial tests for such a model. No changes were required in the model as it was applied to the different polymerization systems for a variety of reaction conditions. The theory offers a unified understanding of the diverse polymerization behavior displayed by such systems.
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1373-1387 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The wettability of poly(ethylene terephthalate) films is an important criterion for their industrial use. The attainment of that property is realized by treatment of the material under corona discharge. The purpose of this article is to describe the influence of the principal parameters of the discharge on the modification of the surface properties; the influence was measured by physicochemical methods (ESCA, contact angle). The results prove that the most important physical parameters of the discharge are the wire-cylinder distance, the current intensity, and the time of treatment. The analysis shows that the fixed species are oxygen and nitrogen in the form of carboxylic functions and amines or nitrogen oxides. In any case, the correlation between free surface energy and concentration of fixed chemical species shows that the surface properties depend on the chemical functions introduced into the material by the discharge.
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1389-1400 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of poly(ethylene oxide) with alkali picrates in tetrahydrofuran and dioxane was studied by optical and NMR spectroscopy and conductance measurements. Evidence was found of the formation of two kinds of solvation complex, differing in the nature of the ion pairs involved. A strong anion effect on cation binding to the polyether was demonstrated.
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  • 62
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1401-1409 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymerization of methylenedioxolanes, such as 4-methylene-1,3-dioxolane (I) and 2,2-dimethyl-4-methylene-1,3-dioxolane (II), with maleic anhydride (Manh) gives rise spontaneously to the alternating copolymers by the participation of charge-transfer (CT) complexes. The formation of CT complexes I-Manh and II-Manh was ascertained by UV and NMR spectroscopies. The equilibrium constants (K) could not be determined but were assumed to be small (K ≪ 1). For comparison with these systems an investigation of I-dimethyl maleate (DMM) and II-DMM systems was carried out to estimate K values 0.115 and 0.157 L/mol, respectively. To clarify the copolymerization mechanism I-Manh-acryronitrile was terpolymerized. Consequently it was concluded that the spontaneous copolymerization of I-Manh and II-Manh systems is effected by the CT complex monomer mechanism.
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  • 63
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 269-291 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new method is presented that provides experimental information which is qualitatively and quantitatively sensitive to assumptions made as to the mechanisms of free radical entry and of latex particle formation in emulsion polymerization systems. The method consists of (1) obtaining (by electron microscopy) the full particle-size distributions (PSDs) at several different times soon after the cessation of latex particle nucleation, (2) using these PSDs to determine the volume dependences of the various rate coefficients governing particle growth by fitting the data to the appropriate evolution equations, and (3) employing these empirical rate coefficients to find that time dependence of the nucleation rate which fits the early-time PSD (again using the evolution equations). This method is quite sensitive to mechanistic assumptions: for example, one is able to determine whether or not the nucleation rate is an increasing or decreasing function of time. The technique is applied to a styrene nucleation system employing sodium dodecyl sulfate as surfactant at well above the critical micelle conventration. The data cannot be fitted even qualitatively by a simple one-step nucleation mechanis, whether it involes micellar entry or homogeneous nucleation. It is found, on the other hand, that the results can be accurately fitted by assuming that coagulation events between primary colloidal particles, perhaps formed by homogeneous nucleation, dominate both the nucleation process and the entry of free radicals into mature latex particles. In addition, the data indicate that the rate of free radical entry into the latex particles decreases with increasing particle size, at least for particles of unswollen radius less than ca. 40 nm.
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  • 64
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 353-364 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 8,9-Benzo-2-methylene-1,4,6-trioxaspiro[4,4]nonane (BMTN) was prepared by the reaction of phthalide with epichlorohydrin, followed by dehydrochlorination. BMTN was polymerized with di-t-butyl peroxide (DTBP) to give a solyble polymer with a high molecular weight and good thermal stability. The infrared (IR) and nuclear magnetic resonance (NMR) spectra indicated that the polymer structure contained aromatic ester and ketone in the backbone. Tg and Tm of homopolymer of BMTN were, respectively, 98 and 282°C. BMTN was also readily copolymerized with such vinyl monomers as methyl methacrylate (MMA), acrylonitrile (AN), and maleic anhydride (MA), but not with styrene, in the presence of radical initiators. AN and MA, in particular, were spontaneously copolymerized with BMTN in the absence of radical initiators at 40°C. From the results of ultra violet (UV) spectra it is suggested that spontaneous copolymerization proceeds via a charge-transfer complex between BMTN as an electron donor and AN or MA as an acceptor.
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  • 65
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    Topics: Chemistry and Pharmacology
    Notes: Carbon-13 Fourier-transform spectra (67.88 MHz) of 1,2-polybutadienes (PBDs) (I-IV) were obtained. The triad and pentad intensities were calculated for the olefinic methylene carbon (C-1). Bernoullian and first-order Markov-chain propagation statistics were tested to fit the experimental data. The pentad placements for the olefinic methine carbon (C-2) were also assigned using the data calculated for the C-1 carbon. Fine-structure splitting due to placements higher than pentads was observed for both C-1 and C-2 carbons in PBD samples III and IV.
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  • 66
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 375-384 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method has been developed for following the bromine and weight losses of fire retarded UPE as a function of temperature. The results obtained by this method indicate that those bromine-containing fire retardants which exhibit a linear LOI-bromine concentration relation, the bromine concentration in the pyrolytically produced fuel remains more or less constant, while for those materials which deviate positively from the linear relation (that is they are more efficient), the bromine concentration in the fuel tends to peak at certain temperatures. When this effect is combined with variation in composition of the pyrolytic fuel, a situation can arise where a high bromine concentration coincides with a fuel particularly sensitive to flame quenching by bromine. Such a combined effect may be the reason why some brominated fire retardants are far more effective than others.
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  • 67
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 397-405 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Anionic solution polymerization of bicyclic oxalactam, 8-oxa-6-azabicyclo[3.2.1]octan-7-one (abbreviated as BOL), at 25°C yields the polyamide with both carbonyl and imino groups at the axial positions in the tetrahydropyran ring. On the other hand, the polyamide obtained by bulk anionic polymerization of BOL at 100°C has more complicated structures, probably due to the isomerizations and side reactions. The most frequent isomerization of the polyamide was the transfer of the carbonyl group adjacent to the tetrahydropyran ring from the equatorial to the axial position in the presence of base or acid catalyst at 25°C. Mechanisms are discussed from the viewpoint of the characteristic bonds in the polyBOL chain.
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  • 68
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 385-395 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Azo compounds such as di(4-hydroxybutyl)-2,2′-azobisisobutyrate, di(3-hydroxybutyl)-2,2′-azobisisobutyrate, di(2-hydroxypropyl)-2,2′-azobisisobutyrate, and di(2-hydroxyethyl)-2,2′-azobisisobutyrate were prepared and used as initiators for the preparation of hydroxyl-terminated polybutadienes (HTPBs) of molecular weight (M̄n) ranging from 2000 to 7500 and functionality between 1.90 and 3.0. The polymers were prepared by free-radical solution polymerization in dioxane and toluene. The polymers obtained were characterized for their molecular weight, hydroxyl number, functionality, and instrinsic viscosity.
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 407-413 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of polymerization of acrylonitrile(AN) initiated by manganese(III) acetate in the presence of glycerol was investigated in the temperature range of 30-40°C. The effect of varying the concentrations of glycerol, sulfuric acid, acetic acid, metal ion, and monomer on the rate was studied. A suitable reaction scheme and rate expression have been proposed. Termination was mutual and was caused by the combination of two growing polymer radicals.
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 415-423 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Linearly segmented polyurethanes and polyurethaneureas are known to be phase separated; one phase is the soft phase, the other, the hard domain. Quantitative evaluation of the degree of phase separation was obtained by DSC. An estimation of the dispersed soft segments outside the soft phase can be made by ΔCp measurements and the increase in glass transition (Tg) can be attributed to the presence of hard blocks in the soft phase. The segregation rate depends on the nature of the soft segments which decrease from hydrogenated polybutadiene to polybutadiene to polyether. It also depends on the nature of the chain extender from aliphatic to aromatic diol and from aliphatic to aromatic diamine. The presence of soft segments in hard domains can be related to the thermoplastic behavior of the polyurethanes and polyurethaneureas.
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 425-433 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of methyl methacrylate (MMA) initiated by an enolizable ketone (R1—CO—CH2—CO—R2)-carbon black system was investigated. Although enolizable ketone itself could not do so, the polymerization of MMA was initiated by enolizable ketone in the presence of carbon black. In addition, a chloranil-enolizable ketone system was able to initiate the polymerization of MMA. It was found that the enol form of the ketone and quinonic oxygen groups on the carbon black surface played an important role in the initiation system; namely, it was considered that the polymerization was begun by the ketone radical (R1—CO—CH—CO—R2) formed by a one-electron transfer reaction from enolate ion to quinonic oxygen groups. The effect of solvent on the process was also studied. The rate of the polymerization increased, depending on the solvent used, in the following order: benzene 〈 1,4-dioxane 〈 dimethyl sulfoxide 〈 N,N-dimethylformamide 〈 N-methyl-2-pyrrolidone. Furthermore, it became apparent that during the polymerization poly(methyl methacrylate) was grafted onto the carbon black surface (grafting ratio was ca. 40% when benzene was used as solvent) and the carbon black obtained gave a stable colloidal dispersion in organic solvent.
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 447-455 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study was made of the formation of polyion complexes between a piperidinium cationic polymer and polyanions and of the binding of azo-dye anions (methyl, ethyl, propyl, and butyl orange) by these complexes. Sodium poly(acrylate), poly(styrenesulfonate), dextran sulfate, and carboxy-methylcellulose were used as polyanions. The resultant polyion complexes (insoluble in aqueous solutions) were compared for their ability to bind the small organic molecules in aqueous solutions, for example, of urea and an inorganic electrolyte (KCI), and exhibited a strong binding affinity toward these small anions. Polyion complexes that consisted of sodium poly(acrylate), dextran sulfate, and carboxymethylcellulose as polyanions cooperated in the binding, whereas the polyion complex of sodium poly(styrenesulfonate) did not. It was suggested that small organic anions interact with the polyion complexes primarily through electrostatic and hydrophobic forces.
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 457-466 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Biphenyl and biphenyl-d10 were coupled by aluminum chloride-cupric chloride. For the two systems, the yields of p-quaterphenyl, p-sexiphenyl, and sublimation residue were compared. The results, which have mechanistic significance, are similar to those reported earlier for benzene versus benzene-d6; that is, a decrease in DP for the deuterated substrate. p-Sexiphenyl, obtained from biphenyl or p-terphenyl and aluminum chloride-cupric chloride, displayed a concentration of 3 × 1017 spins/g in ESR. There was little or no change in spin density after sublimation or crystallization. Even after drastic purification by a variety of techniques the radical character persisted. Biphenyl was polymerized by aluminum chloride-cupric chloride at temperatures in the 50-155°C range. Processable polymers with m- and p-phenylene linkages were produced. When doped with AsF5, the highest conductivity obtained was 7.3 × 10-2 Ω-1 cm-1.
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 435-445 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the presence of many alkylphenols, cationic polymerization of styrene by aluminium chloride leads to low-molecular-weight polystyrenes that contain end groups derived from the phenols. The fraction of phenolic end groups in the polymer is estimated by ultraviolet (UV) measurements to be 40-70% dependent on phenol and the reaction conditions. Phenol is incorporated into the polymer over the whole range of molecular weights (up to 7000). At high phenol concentrations, a significant proportion of the product consists of 1:1 and 1:2 phenol-styrene adducts. The position of attack of the growing carbenium ion on the phenol can be determined by 13C-NMR spectroscopy. With 2,6-dialkylphenols, such as 2,6-di-tert-butylphenol, the high field aromatic resonance near 119.7 ppm is shifted downfield by about 16 ppm when the phenol is incorporated into the polystyrene as an end group. This is interpreted as an exclusive attack of the growing carbenium ion on the 4-position of the phenol. With 2,4-dialkylphenols, such as 2-tert-butyl-4-methylphenol, a corresponding downfield shift shows that reaction occurs only at the 6-position. The preferred site of attack for phenols such as 2-alkylphenols which lack both ortho- and parasubstituents, is the 4-position. With such phenols attack at the 6-position is not excluded. Low-molecular-weight adducts contain 1-methylbenzyl end groups and 13C-spectra are consistent with their presence in the higher-molecular-weight polystyrenes.
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1709-1716 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radiation-induced cationic polymerization of styrene was studied in methylene chloride in the presence of triphenylsulfonium hexafluorophosphate. Acceleration in polymerization and an increase in molecular weight at a low temperature (-78°C) were observed in the presence of triphenylsulfonium salt. A study of pulse radiolysis revealed that both effects are due mainly to PF-6, which forms ion pairs with the cationic species involved in the polymerization.
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  • 76
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    Topics: Chemistry and Pharmacology
    Notes: The composition and gross structural features of plasma polymers formed in the glow regions of an inductively coupled RF plasma with perfluorobenzene and perfluorobenzene/hydrogen mixtures were investigated by ESCA as a function of the operating parameters. The carbon-to-fluorine stoichiometries of the perfluorobenzene polymers are similar and close to those of the starting material but not of the polymers derived from perfluorobenzene/hydrogen mixtures. The rate of film deposition is dependent on the W/FM parameter. Angular and photon energy-dependent studies confirm the vertical homogeneity of the plasma polymer films investigated.
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    Topics: Chemistry and Pharmacology
    Notes: An ESCA investigation has been made of the plasma polymers produced from the isomeric tri-, di-, and monofluorobenzenes in inductively coupled plasmas. Comparison is drawn with other published data on perfluoro-, pentafluoro-, and isomeric tetrafluorobenzenes. The data reveal that extensive molecular rearrangement accompanies polymerization and that proportionately the C:F stoichiometry shows a decrease in fluorine content relative to the monomer in going from perfluoro- to monofluorobenzene. Internal stress, critical surface tensions, and coefficients of friction are compared for the plasma polymers.
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1745-1764 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A multiple-correlation analysis program was used to generate equations relating the Alfrey-Price Q and e values of vinyl monomers to the 13C-NMR absorption frequencies of the α- and β-carbon atoms of the monomers. Separate equations for the calculation of Q and e values of styrenes, chlorinated olefins, acrylates, methacrylates, vinyl ethers, and esters, nitrogen containing monomers, allyl compounds, and miscellaneous olefins were developed. The correlation coefficients of most of these equations were greater than 0.99 and permit accurate calculation of the Q and e values. The Q and e values so calculated may then be used to obtain estimates of the reactivity ratios in copolymerizations prior to actually performing the experiments. Attempts to develop a single Q value equation and a single e value equation for 63 vinyl monomers of the above classes resulted in relations having correlation coefficients of 0.63 and 0.81, respectively, too low to permit sufficiently accurate calculation of the Q and e values.
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  • 79
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1765-1774 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two addition-type polymers, polystyrene and polypropylene, and two condensation-type polymers, poly(ethylene terephthalate) (Mylar) and poly(hexamethylene adipamide) (nylon-6,6), were pyrolyzed directly in the ion source of a mass spectrometer by chemical ionization (CI) to reduce fragmentation. The spectra are relatively easy to interpret because most ion peaks occur at a mass corresponding to the ion formula M±H or M + 3H, where M is the formula of a fragment of the original polymer chain. Oligomer peaks were observed for the addition-type polymers. The intensities of the protonated dimer and monomer were measured as a function of time for styrene (S) and propylene (P). It was found that essentially all the HS+2 was produced by the reaction of HS+ with S, but at least part of the HP+2 was formed by proton transfer to P2. The absence of the analogous reaction in styrene is presumably a result of the reduced volatility of S2.
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  • 80
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1785-1790 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metal phthalocyanine oligomers that possess peripheral carboxylic acid groups were prepared by the reaction of pyromellitic dianhydride, a metal salt, urea, and a catalyst. These materials have blue to purple colors with a metallic luster and are soluble in sulfuric acid, dimethylsulfoxide, dimethylformamide, and dimethylacetamide. Their thermal stability is high in an anaerobic atmosphere with char yields of 80-85% at 800°C. Elemental, spectral, and titrimetric analyses and thermal studies were carried out to characterize them.
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  • 81
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 541-556 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The optical properties of poly(vinylamine) containing optically active (+)- or (-)-2-(thymin-1-yl) propionyl groups as grafted pendants (PT) and the related monomer (MT) and dimer models (DT) were investigated by UV, circular dichroism (CD), and NMR spectroscopy. Highly syndiotactic PT has a smaller hypochromicity versus MT and a larger optical rotation than the less syndiotactic PT in various solutions. These results are attributed to an interaction between the configurational arrangement of thymines, the conformation of the polymers, and base stacking between thymines. The interactions of these polymers with poly(adenylic acid) (polyA) were also studied and the results compared with other vinyl-type nucleic acid model polymers. The isomers of the optically active dimer models [prepared from meso and (dl)-2,4-diaminopentane] were separated. The CD spectra of (+)-D(-)T in CHCl3 and trifluoroethanol (TFE) displayed extremely solvent-dependent exciton coupling of the π-π* (B2u) transition of the base chromophore, which was not observed in the other models or polymers, except the meso-type dimer model (meso)-D-(-)T. This coupling decreased with increasing solvent dielectric constant, while UV hypochromicity increased. This behavior as well as the 360-MHz NMR spectra suggest that (+)-D(-)T exists in an extended form in solvents of low dielectric constant and gradually assumes a stacked conformation as the dielectric constant increases.
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  • 82
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4,4′-Bis(N2)-{4-[4-(2,3-bicyclo-[2.2.1]hept-5-ene-dicarboximido)phenoxy]-phenyl(-aspartimido)-di-phenyl ether (2NAD/1020) and various similar polymer percursors were synthesized from bismaleimides by the Michael addition of two moles of aromatic diamine followed by end capping of the resultant amino-terminated bisaspartimide groups with nadic anhydride. These precursors were characterized by using Fourier-transform infrared (FT-IR), proton, and carbon-13 nuclear magnetic resonance spectroscopies (1H- and 13C-NMR). Thermal polymerization of 2NAD/1020 by heating it above its melting point gave a reddish brown thermoset polymer. The curing behavior and thermal stability of these nadimides were evaluated by differential scanning calorimetry and thermogravimetric analysis studies. Graphite fiber laminates were prepared from these polymer precursors and their mechanical properties evaluated. Gas Chromatography/Mass Spectra of the precursors and thermosets have given an understanding of their decomposition behavior. The structures of the thermosets were examined by FT-IR spectroscopy.
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  • 83
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 599-601 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 84
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 579-588 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Binding of the cationic dye auramine O (AuO) to the polysoap-type polymers poly(vinylbenzo-18-crown-6) (P18C6) and polyvinylbenzoglyme (PVBG) in water were studied by fluorimetry and dialysis. The quantum yield of P18C6-bound AuO was found to be 0.028, the value being 0.018 for AuO bound to PVBG. The intrinsic binding constants were found to be 2.2 × 104M-1 (P18C6) and 1.2 × 104M-1 (PVBG), the respective first binding constants being 317 and 63M-1. Addition of crown-ether-complexable cations such as K+, Tl+, or Cs+ converts the neutral poly(crown ether) into a polycation, causing repulsion of the cationic dye and a strong decrease in the AuO fluorescence. AuO fluorescence was also studied in the absence of polymer in ether solvents, giving θ values of 0.011 and 0.018 in THF and dioxane. Traces of water rapidly form a nonfluorescent species. Solutions of AuO in water without polymer present exhibit very strong fluorescence on addition of BPh4 anions owing to formation of AuO+, BPh4- ion pairs and higher aggregates.
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  • 85
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 589-597 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal reactions of pure metal(11) 4,4′,4″,4′″-phthalocyanine-tetracarboxylic acids of copper, cobalt, and nickel at 350-400°C in vacuum have been studied using Fourier transform infrared spectrometry, gas chromatography, and mass spectrometry. Based on these observations, novel in situ reactions for the synthesis of heat-resistant phthalocyanine “sheet” polymers are described. The poly(metal phthalocyanine) polymers of copper, cobalt, and nickel so synthesized have been characterized by elemental analysis, infrared spectroscopy, and dynamic thermogravimetric analysis. The most noteworthy property of these polymers is their extreme resistance to heat in an anaerobic atmosphere and their high char yields (89-93%) at 800°C in a nitrogen atmosphere.
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  • 86
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 603-607 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 87
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 609-613 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 88
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 615-621 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 89
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 623-626 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 90
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1875-1884 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The laser-initiated polymerization of charge-transfer monomer complexes was investigated with a pulsed nitrogen laser and an argon laser. Several donor-acceptor monomer charge-transfer systems were screened for polymerization in different solvents. Polymerization by laser initiation was achieved in two of these systems; that is, 2-vinylnaphthalene/fumaronitrile and 9-vinylanthracene/fumaronitrile. The best polymer yields were obtained with the 2-vinylnaphthalene/fumaronitrile system in sulfolane solvent. The influences on the polymer yield and composition of solvents, varying focal path length, glass conditioning, initiation sources, environment, and monomer feed ratios were evaluated. Infrared (IR) spectral studies, gel permeation chromatography (GPC), and chemical analyses were performed to characterize the polymer products arising from the polymerization of 2-vinylnaphthalene/fumaronitrile in sulfolane. The polymer contained a high percentage of sulfolane (ca. 1/3 mol fraction), presumably arising from solvent transfer to the growing polymer chains during the propagation phase of the polymerization.
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  • 91
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 651-670 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dissolution process and some solution properties of cellulose in mixtures of liquid ammonia (NH3) and ammonium thiocyanate (NH4SCN) are discussed. The mole fraction ratio of NH3, NH4SCN, and H2O which dissolve cellulose were determined. The effect of temperature on several solution properties was also examined. The temperature coefficient d In [n]/dT for the limiting viscosity number [n] has a value of -1.58 × 10-2 °C-1. This is considered to be rather large but is, in fact, a common occurrence for almost all cellulose derivatives in solution. The values for the Huggins constant K′ showed no systematic trends with temperature. They did, however, suggest the presence of considerable association of the cellulose in solution. Miscibility results of adding the cellulose solutions to organic liquids are also reported.
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  • 92
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 637-649 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New active bisamides, 4,4′ -diacylbis-2-aryl-1,3,4-oxadiazoline-5-thiones and -ones having various electron accepting groups in the oxadiazoline units were synthesized, and their reactivities toward diamines were investigated. The polycondensation reactions of the bisamides derived from 2-aryl-1,3,4-oxadiazoline-5-thiones with both aliphatic and aromatic diamines occurred rapidly even at room temperature to form high-molecular-weight polyamides in quantitative yields. The reactivities of the bisamides having electron accepting groups such as p-chloro and p-nitro groups, particularly p-nitro groups, toward diamines were much higher than that of the corresponding bisamide having no such group. It was also found that reaction conditions such as solvent, monomer concentration, and temperature had a strong influence on the molecular weight of the resulting polyamides. Aminolysis of several benzoyl derivatives of 2-aryl-1,3,4-oxadiazoline-5-thiones and -ones was also carried out as a model reaction, and the effect of electron accepting groups on the reactivity of these compounds was discussed.
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  • 93
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 671-677 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A two-phase polycondensation reaction was used to prepare high molecular weight linear poly-(amino-s-triazine)s from aminodichloro-s-triazines and diamines. These polymers contain a high concentration of melamine-type units in the polymer backbone. Molded specimens exhibited good mechanical properties and resistance to organic solvents. Dimethyl substitution at the exocyclic amino group led to a significant reduction in indentation resistance, strength, and modulus.
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  • 94
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    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 679-689 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of flame retardant (FR) action of red phosphorus in polyacrylonitrile combustion was investigated by thermogravimetry, flash-pyrolysis GC-MS, and combustion methods. Red phosphorus was found to increase the thermal stability in air of polyacrylonitrile and to induce a char residue increment on this substrate. Both these effects disappeared when pyrolysis was carried out under nitrogen flow. Flash-pyrolysis GC-MS experiments showed that red phosphorus does not alter the pyrolysis product distribution of polyacrylonitrile, which implies that there is no specific interaction between polyacrylonitrile and red phosphorus. These data also showed that polymeric red phosphorus decomposes to volatile white phosphorus (P4) during pyrolysis. These observations allow us to propose a simple model for the mechanism of FR action of red phosphorus on polyacry-lonitrile at the molecular level. Combustion data for polyacrylonitrile-red phosphorus mixtures are in agreement with the proposed mechanism of FR action.
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  • 95
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1949-1952 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 96
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1947-1948 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 97
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1953-1957 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 98
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1959-1963 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 99
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1965-1970 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 100
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    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 1971-1984 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Volume flow of epoxide prepolymers and the effect of compression rate, temperature, and molecular weight on it are described. An increase in longitudinal volume viscosity with decreasing volume deformation, increasing compression rate, and increasing temperature has been observed. The molecular weight seems to have no influence.
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