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  • 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
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1-11 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dispersion polymerization of styrene in the particle size range of 10 μ with lauroyl peroxide as initiator results in a double-peak molecular weight (MW) distribution. The high-MW fraction was due to emulsion polymerization. The same phenomenon also exists in AIBN and benzoyl peroxide initiation, although it is less obvious. The kinetics of the reaction for dispersion polymerization was dependent on the concentration of the dispersing agent and the nature of the initiator.
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  • 3
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The plasma polymers formed in glow and nonglow regions of an inductively coupled RF plasma with perfluorobenzene and perfluorocyclohexane are discussed as a function of operating conditions of the plasma by means of ESCA. The core levels of the plasma polymers are shown to be strikingly different but characteristic of a well-defined but complex polymerization scheme. For the nonglow regions fluorine incorporation is shown to be greater than for polymers prepared in the glow regions and a preponderance of CF2 features is apparent. Perfluorobenzene deposits polymer faster than perfluorocyclohexane and changes in component composition of the C1s profile are studied as a function of operating conditions of the gas plasma.
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  • 4
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: MoCl5, WCl6, and OMoCl4 were found to be effective initiators for the polymerization of acetylene and its monosubstituted derivatives RC=CH. The polymerization proceeded in homogeneous and heterogeneous media and was carried out in nonpolar (chloroalkanes, aromatic hydrocarbons) and polar (THF, acetone, dioxane, carboxylic acids) solvents to give a high yield of polymers.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 47-51 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this investigation an approach to correlate the composite rate constants of some redox polymerization reactions [acrylonitrile-Ce(IV)-organic substrate] with a new type of multiparameter equation is described. The multiparameter equation is based on Swain and Lupton's F and R, the field and resonance components of the substituents, respectively, and the unique positional weighting factors f and r suggested by Williams and Norrington. The statistical parameters of the correlation involving the substituent constants (fF and rR) and the rate data have been found to be quite satisfactory, the average coefficient of determination being 0.91. The significance levels of the correlation also indicate that the present model is applicable to the kinetics of redox polymerization. The sign and magnitude of the reaction-dependent regression constants α and β suggest that three different types of reaction mechanisms are operative for the substrates benzaldehyde, phenylthiourea, acetophenone, and toluene.
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  • 6
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four solvents of cellulose have been studied by using 13C-NMR spectroscopy. All these solvents, N-methyl morpholine-N-oxide, methylamine, hydrazine, and paraformaldehyde (PF), contained dimethyl sulfoxide (DMSO) as a cosolvent. Oligomers of cellulose of DP = 10 soluble in hot DMSO have been used as model compounds. 13C chemical shifts and line shapes show that three of the mentioned solvents are “true solvents” of cellulose. On the other hand, dissolution of cellulose in DMSO-PF system occurs by the formation of a statistical derivative of cellulose. Enriched 13C bacterial cellulose on C-1 and C-6 positions have been used to identify the 13C positions mainly in DMSO-N-methyl morpholine-N-oxide system. This solvent has been found to be degradative for the macromolecule when the solution is kept at 100°C over a long period. Viscosity measurements show a reduction of the molecular weight in these conditions. Polarimetry indicates that no glucose is present in solution and hence there is a statistical break of the chain. Enriched cellulose solution in DMSO-N-methyl morpholine-N-oxide has been also used for relaxation time (T1) determination both of the solvent and of the enriched carbons of the polymer. Nuclear Overhauser enhancement (NOE) was found to be 1.8 for C-1 and 2.1 for C-6 showing that relaxation phenomenon is not purely dipolar. T1 values of 97 and 65 msec are found for C-1 and C-6 of cellulose, in good agreement with the values known for polysaccharides. Determination of T1 for the different carbon atoms of the solvent DMSO-N-methyl morpholine-N-oxide with and without cellulose shows a large reduction of T1 for N-methyl morpholine-N-oxide molecule. This denotes a slower molecular motion of this molecule and a preferential interaction with the cellulose macromolecule.
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  • 7
    Electronic Resource
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 109-121 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vinyl fluoride was polymerized by photochemical initiation in a continuous-flow cylindrical reactor at room temperature and at pressures of up to 30 atm. Copolymers with vinyl acetate were prepared in order to improve the solubility and processability of poly(vinyl fluoride) (PVF). The copolymers were hydrolyzed to the corresponding vinyl alcohol copolymers and yielded hydrophilic films that are strong and flexible only when swollen by water. It was found that on hydrolysis the Tg, Tm, and heat of fusion as well as degree of crystallinity increased. It was suggested that PVF and the copolymers with vinyl alcohol are isomorphous.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 147-155 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solution and solid-state thermal cis-trans isomerization of cis-transoidal polyphenylacetylene was investigated. At temperatures higher than 120°C, cis-trans thermal isomerization in solution is accompanied by cyclization, aromatization, and scission of the polymer chain. Both spectral and kinetics data showed that at temperatures lower than 120°C, not only cis-trans thermal isomerization takes place but also intramolecular cyclization.
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  • 9
    Electronic Resource
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 157-168 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Direct fluorination of the hexafluoroacetone-ethylene copolymer, [CH2CH2OC(CF3)2]n, under conditions designed to promote fragmentation of the polymer chain has led to the synthesis of a number of structurally unusual branched perfluoropolyethers [—CF2—CF2—O-C(CF3)2—]n. These new perfluoropolyethers have been characterized by 19F-NMR, and their physical properties are reported. Direct fluorination under milder conditions yields a high-molecular-weight perfluoropolyether.
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  • 10
    Electronic Resource
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 179-189 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bulk polymerization of isobutyl vinyl ether was studied at 25°C in a wide dose rate range, 8.2-277 rad/sec by γ rays and 8.8 × 103-2.2 × 105 rad/sec by electron beams. At low dose rate, 8.2-277 rad/sec, only the radical polymerization took place. At high dose rate exceeding 8.8 × 103 rad/sec, cationic polymerization was found to occur in addition to the radical polymerization. DPn of the product at high dose rate was 9-10. Further drying of the monomer increased Rp, and molecular weight of the product formed by cationic mechanism also increased.
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  • 11
    Electronic Resource
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 169-178 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radiation degradation behavior of methyl α-chloroacrylate (MCA) and methacrylonitrile (MCN) copolymers has been investigated as part of a program to develop high-sensitivity polymeric resists for integrated circuit manufacture. High-molecular-weight copolymers were prepared by emulsion techniques. Several different copolymer compositions were prepared varying from 19 to 68 mole % MCA. These copolymers were fractionated and then subjected to γ irradiation from a 60Co Source. The Gs - Gs, Gs - 4Gs values were determined from M̄;F〉nk-1 and Gu-1 versus dose plots, and the Gfs and Gs Values were then calculated. Molecular weights of both unirradiated and irradiated polymers were analyzed by membrane osmometry and gel permeation chromatography. All copolymers exhibited higher degradation susceptibilities than that of poly(methyl methacrylate) (PPMA), which has Gx = 1.3. The individual Gx and Gx values of the copolymers were found to fall between those of the two homopolymers, poly(methyl α-chloroacrylate) (Gx = 6.0) and polymethacrylonitrile (Gx ∼ 3.1). The dependence of Gx and Gx values on molecular weight was minor. The crosslinking susceptibility of the poly(methyl α-chloroacrylate) (Gx ∼ 0.8), was greatly decreased by copolymerization with MCN. Relatively small amounts of MCN caused a large drop in Gx, i.e., Gx ∼ 0.15 at 32% MCN and Gx ∼ 0.03 at 51% MCN. The observation could be attributed to the decreasing probability that crosslinking sites, in the MCA monomer units on adjacent chains, would lie in close proximity.
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  • 12
    Electronic Resource
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 191-202 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bulk polymerization of α-methylstyrene was carried out in a wide dose rate range, 7.6-256 rad/sec by γ rays and 8.5 × 103-2.1 × 105 rad/sec by electron beams. At high dose rate by electron beams, cationic polymerization took place along with formation of oligomeric product of DPn = ∼4. At low dose rate by γ rays, radical polymerization was found to occur in water-saturated monomer. The cationic polymerization at high dose rate proceeds with essentially the same mechanism as was already known in γ-ray polymerization of dry monomers. Relatively low reaction rate of the cationic polymerization compared with that of styrene is explained with the fact that the propagation of α-methylstyrene is much more easily inhibited by a slight amount of water.
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  • 13
    Electronic Resource
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 223-233 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New polymeric cinchona alkaloids having favorable structures and properties for asymmetric catalysts have been prepared by radical copolymerization of the alkaloids with acrylonitrile using azobisisobutyronitrile (AIBN) as an initiator. Of the many reaction solvents tried, dimethylformamide (DMF) was found to be the solvent of choice especially for a large-scale synthesis. Alkaloid monomers employed were free dalkaloids, such as quinine, quinidine, cinchonidine, and cinchonine, and modified ones including 9-O-ethoxycarbonylquinine and quinine salts. The copolymers were thermally stable powders, soluble in DMF and DMSO, and insoluble in common organic solvents. They were found to be converted into water-soluble polymeric alkaloids by hydrolysis with alkaline hydrogen peroxide.
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  • 14
    Electronic Resource
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 241-249 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A previously developed model which has been used to describe the kinetic behavior of free radical polymerization in the region of the gel effect is here subjected to a detailed quantitative examination. It is shown, using data for the polymerization of methyl methacrylate, that the quasi-steady-state assumption is valid during the gel effect, and that the model provides a good description of the chain lengths and concentrations of different species present in the reaction. The postulate that primary radical termination becomes important as the gel effect advances is tested and found to be true.
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  • 15
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 251-257 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Six recently proposed methods for analyzing copolymerization composition data have been compared to a nonlinear least-squares analysis to ascertain the precision of the six methods in determining reactivity ratios. Data used were simulated for five hypothetical monomer pairs with three different types of experiment design and contained error structures similar to those observed experimentally. The results of the comparisons suggest that retrospective analyses of existing copolymerization data should only be done with a nonlinear least-squares analysis. For new data, the design of experiments is of great importance, and when done properly allows the use of some of the linear least-squares methods of analysis.
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  • 16
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 275-281 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method of determining the degree of hydrolysis by potentiometric titration of polyacrylamide (PAA) with HCl and NaOH was developed. From the titration curves and the control of the degree of purity it is possible to calculate the level of hydrolysis and the quantity of pure acid contained in the PAA of a commercial product.
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  • 17
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 355-357 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 18
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 349-353 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 19
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 371-372 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 20
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 365-370 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 21
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 22
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 527-531 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Results are presented which extend earlier findings on the transformation of insoluble crosslinked polysiloxanes into soluble linear polymers by selective aminolysis at crosslink sites. The present study provides evidence of a substantial steric effect and catalysis by 2-pyridone. The results with 2-pyridone are attributed to tautomeric catalysis which, to our knowledge, had not been observed before in substitution reactions at silicon. Evidence is also presented that unhindered, difunctional primary amines effect aminolysis with both amine groups to produce insoluble crosslinked polymer, presumably with silylamine functionality at crosslink sites.
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  • 23
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1085-1090 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The behavior of viologen polymer (P-V2+) as an electron transfer catalyst in the reaction of hydrogen generation was studied. In the photoirradiation system, which contains triethanolamine (TEA), Ru(bpy)3+3, and P-V2+, the amount of hydrogen evolution was less than methyl viologen (MV2+); P-V2+, however, was more effective in sodium dithionite as the electron donor and showed higher initial rates than MV2+.
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  • 24
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1091-1099 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymer(Poly A) which contains alloxan moiety was prepared by the oxidation of the copolymer of allyl barbituric acid and vinyl acetate with chromium trioxide. The photoreduction of Poly A by ultraviolet (UV) irradiation was used to isolate the polymer(Poly A·) in which the alloxan radical was present. The properties of this polymer(Poly A·) thus obtained were investigated. Poly A was also reduced by chemical agents to obtain the polymer(Poly D) which had a dialuric acid structure.
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  • 25
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1101-1108 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The formation of complexes between ZnCl2 and methyl methacrylate (MMA) or between ZnCl2 and AIBN was tested at two different polymerization temperatures, taking into account the Haeringer and Riess treatment. For any concentration of ZnCl2 between 0.01 and 0.1 mole/liter the formation of ZnCl2-MMA complexes is favored, whereas AIBN-ZnCl2 complexes are hardly showed. The effect of zinc chloride on the stereostructure of poly(methyl methacrylate) was also investigated at both temperatures.
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  • 26
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1109-1117 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Iron(III) proto-porphyrin IX dimethyl ester (HDME) can copolymerize with π-conjugated monomers binding at one end of the polymer chain. Apparent Q, e values of HDME were Q = 70 and e = -0.17. The copolymerization of HDME with π-unconjugated monomer was feasible by using π-conjugated monomer as a third component. When unconjugated vinylimidazoles were used as monomers, the obtained ternary copolymers of HDME formed intramacromolecular complexes of iron(II) porphyrin with vinylimidazole residues, which gave stable carbon monoxide adducts.
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  • 27
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1133-1145 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-substituted poly(p-phenylene terephthalamide)s (PPTA), such as N-alkylated, N-aralkylated, and N-carboxymethylated poly(p-phenylene terephthalamide), were synthesized from PPTA and the corresponding halides by the polymer reaction via the metalation reaction in a solution of sodium methylsulfinylcarbanion in dimethyl sulfoxide at low temperature. The introduction of various substitutional groups into the amide groups of PPTA increased their solubilities, but decreased their thermal stabilities compared with PPTA. The effects of various substitutional groups on the thermal properties and the solubilities are discussed. Liquid crystal formation was noticed for PPTA substituted with bulky groups such as 9-anthrylmethyl group.
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  • 28
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1119-1132 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactivity ratios of 180 published oxonium copolymerization systems have been reviewed in terms of the extended Kelen-Tüdos method. Only 32 (17.8%) systems were described in sufficient detail for reevaluation and classification. r Values, together with their 95% confidence limits have been calculated. A quantity δ□, suitable for classification of the systems, has been introduced. Of the 32 reevaluated systems, five were found to belong to class I and 14 to class I(!), i.e., 19 systems for which the conventional copolymerization equation was found to be adequate. Class II systems were not found. Finally, 13 systems were judged to belong in class III, i.e., systems for which the experimental data are inconsistent and the published r values meaningless.
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  • 29
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1147-1153 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of acrylonitrile initiated by the redox system 2,2′-thiodiethanol/Ce4+ in dilute sulfuric acid was investigated in the temperature range of 15-25°C. Oxidation of the substrate in the absence of the monomer has also been studied. The reaction involves the formation of an intermediate complex between the metal ion and the protonated species of the reductant, whose decomposition gives rise to the initiating free radicals. Multual interaction of the growing macroradicals accounts for the termination of polymerization. A suitable kinetic scheme has been proposed and rate and equilibrium constants evaluated.
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  • 30
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1155-1166 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of polyesters containing conjugated diacetylenic groups in the polymer backbone were synthesized by interfacial condensation of 3,5-hexadiyne-1,6-diol and diacid chlorides of succinic, glutaric, adipic, azealic, sebacic, terephthalic, and isophthalic acids. The polyesters were characterized by their infrared and ultraviolet absorption spectra, elemental analysis, and viscosity measurements. Powder x-ray patterns indicated high degress of crystallinity. The polyesters were found to be highly photoreactive. The relative photoreactivities of the polyester films were determined by the adhesion method. Only small differences in the reactivity have been observed despite structural changes in the R group in the polymer backbone. Differential thermal analysis behavior of all polymers in the temperature range ambient to 300°C and isothermal behavior of HGI at two different temperatures have been studied.
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  • 31
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1167-1174 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polystyrene of narrow molecular weight distribution, Mw/Mn ≈ 1.03, was subjected to γ irradiation at 100 and 150°C. The yields of scission and crosslinking, G(S) and G(X), where determined from the changes in molecular weight distribution using gel permeation chromatography, (GPC) with supporting evidence from osmometry and viscometry. The ratio G(S)/G(X) increased from 0.02 at 30°C, obtained previously, to 2.8 at 150°C. This was mainly due to a tenfold increase in G(S), whereas G(X) apparently decreased slightly. These results are compatible with increased disproportion of chain scission radicals relative to their combination, analogous to the temperature dependence of mutual termination in the free radical polymerization of styrene. There was no obvious discontinuity through the glass transition temperature, although there may be a change in sign of the temperature coefficient of G(X). This system provides an excellent example of the applicability of measurements of molecular weight distributions and averages to determinations of G(S) and G(X) under conditions when gel measurements are inappropriate, either because of the failure of the system to form gel, or, as in the present case, because of the very large radiation doses required for gel formation.
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  • 32
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This work investigates spontaneous gelatination of polysulfonamide in the solution of dimethylacetamide by nuclear magnetic relaxation, small-angle light scattering, and refractive index measurement. Two stages of the gelatination process were found to occur. Spherulites are formed in the first stage while the mobility of the solvent molecules decreases sharply. The second stage is characterized mainly by perfection of the inside structure of spherulites without a change in their size. The degree of decreasing mobility of the solvent molecules is much less in this stage than in the first stage.
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  • 33
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1175-1196 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A structural study of furan-maleic anhydride copolymer (F-MAH) was undertaken to confirm its alternating nature and to determine its microstructure. The spectral properties of a model compound representing the alternating repeat unit, 2-(2-tetrahydrofuranyl)succinic anhydride, were compared with those of F-MAH. Their infrared (IR), 1H, and 13C nuclear magnetic resonance (NMR) spectra (after compensating for the absence of the olefinic double bond) were in good agreement with those of the copolymer. Furthermore, the observed splitting in the 1H- and 13C-NMR spectra of F-MAH were assigned to cis-trans linkages on both the F and MAH units, with cis linkage being favored on both units, especially the former. The structure of 2,5-dimethylfuran (DMeF)-MAH copolymer is similar to that of F-MAH copolymer, except that the preference of cis linkages is less pronounced. The structure of 2-methylfuran (MF)-MAH copolymer is a complex structure with numerous 2,3-furandiyl units. A mechanistic study was undertaken to elucidate the roles of F-MAH Diels-Alder adduct, and the charge-transfer (CT) complex in the radical initiated copolymerization. The adduct reverted substantially to monomers under the reaction conditions; but, the amount of adduct remaining at equilibrium was quite appreciable; therefore, its participation could be ruled out on this basis alone. However, on polymerizing the adduct in the presence of F-d4, the latter was incorporated into the copolymer to an extent indicative of free monomer exchange. Therefore, the adduct cannot be directly involved in the polymerization.
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1203-1215 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to identify the factors causing an agitation effect on the rate of soapless emulsion polymerization, the polymerization of methyl methacrylate was carried out in water. Experimental results indicated the significance of monomer transfer from monomer droplets to water. A kinetic model was proposed which would take into account this monomer transfer. This model enabled the effect of monomer transfer on the rate of soapless emulsion polymerization to be evaluated for the present system and the experimental results to be interpreted qualitatively.
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1217-1223 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gamma irradiation at liquid nitrogen temperature of dicyclopentadiene, 2-methylennorbornene, and cyclopentadienyl-5-endo-norbor-2-enyl-methane-based ethylene-propylene terpolymers leads to the formation of macroradicals of the alkyl type by loss of hydrogen atoms from the ethylene-propylene chains. When warmed almost to glass transition temperature these primary alkyl species decay and generate new radicals by the double-bond addition and/or H abstraction from the unsaturations. The nature of the radical products was determined by ESR and MO methods.
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1239-1249 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Crosslinked poly(3,4-pyrrolidinediylethylene)s with functional side chains that contain acid and ester groups were synthesized by a number of different methods and the structures of the various resins were compared by 13C-NMR studies. The advantages and problems of this technique for structural determination of crosslinked polymers are compared with those methods normally used; for example, infrared (IR) and elemental analysis. Preliminary selective metal chelating abilities of the resins were determined.
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1225-1238 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of acrylamide initiated by an ascorbic acid-peroxydisulfate redox system was studied in aqueous solution at 35 ± 0.2°C in the presence of air. The concentrations studied were [monomer] = (2.0-15.0) × 10-2 mole/liter; [peroxydisulfate] = (1.5-10.0) × 10-3 mole/liter; and [ascorbic acid] = (2.84-28.4) × 10-4 mole/liter; temperatures were between 25-50°C. Within these ranges the initial rate showed a half-order dependence on peroxydisulfate, a first-order dependence on an initial monomer concentration, and a first-order dependence on a low concentration of ascorbic acid [(2.84-8.54) × 10-4 mole/liter]. At higher concentrations of ascorbic acid the rate remained constant in the concentration range (8.54-22.72) × 10-4 mole/liter, then varied as an inverse halfpower at still higher concentrations of ascorbic acid [(22.72-28.4) × 10-4 mole/liter]. The initial rate increased with an increase in polymerization temperature. The overall energy of activation was 12.203 kcal/mole in a temperature range of 25-50°C. Water-miscible organic solvents depressed the initial rate and the limiting conversion. The viscometric average molecular weight increased with an increase in temperature and initial monomer concentration but decreased with increasing concentration of peroxydisulfate and an additive, dimethyl formamide (DMF).
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  • 38
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1251-1259 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of acrylonitrile in the presence of systems that consisted of triphenylphosphine (PPh3) and a Lewis acid RmMXn (ZnCl2, Me3Al, Et3Al, Et2AlCl, EtAlCl2, AlCl3) was studied. The systems that contained Me3Al and Et3Al (i.e., Lewis acid of moderate acidity) were the most efficient catalysts. Conductometric measurements carried out in the polymerization systems showed the presence of ions. The presence of phosphonium cation in the polyacrylonitrile chain formed by the PPh3-RmMXn catalytic systems was determined by IR, 1H-NMR, and 31P-NMR spectroscopy. The average molecular weight measurements and kinetic chain lengths of polyacrylonitrile formed within the reaction time in the presence of PPh3-Et3Al showed that transfer reactions occur. According to the results obtained, the polymerization reaction of acrylonitrile by PPh3-RmMXn involved a zwitterion formed by the attack of PPh3 on acrylonitrile complexed by Lewis acid [Ph3P⊕—CH2—C⊖H—C≡N → MRmXn] and the anion [CH2=C⊖—C≡N] formed by the proton abstraction from the monomer.
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1261-1264 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1269-1272 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1273-1277 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1279-1282 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 949-958 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of polymer-polymer interaction was made on several poly-L-lysines that contained pendant nucleic acid bases substituted on the N′ position. Conformation and interaction of these polypeptides were studied in solution by spectroscopic measurement. The results obtained suggest that the high-molecular-weight polymers form polymer complexes in a helical conformation by specific adenine-thymine base pairing. On the other hand, no interaction could be observed for the low-molecular-weight polymers, which existed in a random coil structure.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 959-965 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polydimethylsilylene is a largely crystalline, high-melting polymer that is soluble only above 200°C and does not thermoform below its decomposition temperature. Introduction of ethyl and propyl substituents into the linear silylene system by random copolymerization of dimethylsilylene with ethylmethyl- and methylpropylsilylenes leads to tractable polymers that are soluble in common solvents at normal ambient temperatures.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 967-985 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The transport of oxygen by diffusion from the environment into a gas stream was investigated as a model for the analogous process in a diffusion flame. The amount transported at steady-state conditions depended on the flow rate, diameter, and spatial orientation of the gas stream. A change of the same extrinsic parameters in a diffusion flame caused changes of burner surface temperature, maximum flame temperature, and flame height. These responses were correlated and yielded an overall activation energy of the rate-controlling reaction step in the combustion process equal to 49 kcal/mole. This value was the same for several types of diffusion flames examined and appeared to be associated with the CO/CO2 conversion process at the high-temperature flame boundary. Flame quenching was demonstrated to occur at a minimum fuel flow rate and minimum environmental oxygen concentration which were characteristic for a given fuel. Quenching conditions were related to the diffusion rate of oxygen into the product effluent stream. Quenching of a polymer flame by depletion of environmental oxygen was governed by the same processes. The effect of extrinsic parameters on polymer flames is discussed in Part II.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1021-1034 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On irradiation with ultraviolet light, dialkyl-4-hydroxyphenylsulfonium salts undergo reversible photodissociation and in the process generate ylids and Brønsted acids. When the anions are nonnucleophilic in character, as, for example, BF4-, AsF6-, PF6-, and SbF6-, the strong acid which is produced is capable of initiating cationic polymerization. The polymerization of several monomers was carried out to demonstrate the general applicability of these new photoinitiators.
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1291-1299 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photopolymerization behavior of p-phenylene diacrylic acid dimethyl ester (p-PDA Me) crystal and the thermal behavior of the resultant poly-p-PDA Me were investigated. From the kinetic study of polymerization at various temperatures a topochemical process via a stepwise mechanism was observed. Continuous change from monomer to polymer crystals was demonstrated by x-ray diffraction pattern and DSC analysis. Crystallinity of the reacting phase was maintained at an extremely high degree during the polymerization process in support of monomer crystal lattice control. Thermal study on as-polymerized poly-p-PDA Me crystal confirmed that the thermal reaction was a polymer crystal lattice-controlled depolymerization, which was followed by miscellaneous processes that involved vaporization, sublimation, and deterioration of the oligomeric or monomeric units of p-PDA Me. Thermal stability was dependent on the molecular weight. All the results are compared with those of four-center-type photopolymerization in the crystalline state.
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1329-1336 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of pentaerythritol (1) or dipentaerythritol with caprolactone yields prepolymers of the general structure \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm C} { \left( {\rm CH}_2 {\rm OH} \right)_4 } \hbox{--} {\rm i} \left [ {\rm CH}_2 {\rm O} \left( {\rm COCH}_2 {\rm CH}_2 {\rm CH}_2 {\rm CH}_2 {\rm CH}_2 {\rm O} \right)_{\rm n} {\rm H} \right]_{\rm i}$$\end{document} for i = 1, 2, 3, and 4 (2)-(5). The 13C chemical shifts of the quaternary carbons in (1)-(5) differ by more than 0.5 ppm. Conditions were determined to obtain quantitative intensity ratios of these carbons. The relative intensities give the distribution of the various branched structures and permit calculations of the average number of caprolactones per branch. Results are reported for caprolactone/polyol mole ratics of 3-66.
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1349-1356 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methods of synthesis of benzils were considered and some new combinations of old reactions were developed to make these materials more readily available as polymer intermediates.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1035-1046 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diethynylphenyl ether (DEPE) was synthesized and its thermal polymerization studied by NMR, IR, and DSC techniques. DEPE is a crystalline solid that melts at 72-73°C and undergoes polymerization beginning at about 150°C. The heat of polymerization measured by DSC was 53 ± 2 kcal/mole. Thermomechanical analysis (TMA) of the fully cured resin showed softening behavior at temperatures in excess of 400°C. Weight loss up to 720°C was only 21%. A mechanism of polymerization based on the analysis of IR and NMR data for party polymerized material below 300°C is proposed.
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  • 52
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    Topics: Chemistry and Pharmacology
    Notes: A series of N-methyl-substituted aromatic polyamides derived from the secondary aromatic diamines 4,4′-bis(methylamino)diphenylmethane, 3,3′-bis(methylamino)diphenylmethane, 4,4′-bis(methylamino)benzophenone or 3,3′-bis(methylamino)benzophenone and isophthaloyl dichloride, and terephthaloyl dichloride or 3,3′-diphenylmethane dicarboxylic acid dichloride was prepared by high-temperature solution polymerization in s-tetrachloroethane. Compared with analogous unsubstituted and partly N-methylated aromatic polyamides, the full N-methylated polyamides exhibited significantly lower glass transition temperatures (Tg), reduced crystallinity, improved thermal stability, and good solubility in chlorinated solvents.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1071-1078 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A wide compositional range of copolymers of 1-cyclobutene carbonitrile (CBCN) and 1-bicyclobutance carbonitrile (BBCN) with common vinyl monomers was prepared in order to study systematically the effect of cyclobutane carbonitrile ring incorporation on the glass transition temperature (Tg). In general, the Tg's of the copolymers are increased in proportion to the weight percent of the small-ring monomer incorporated, but the 1,2-mode of incorporation raises Tg more than the 1,3-mode. Attempts were made to correlate data with quantitative Tg-composition relationships (Fox-Johnston equations). Prediction for nitrile homopolymer Tg's are compared with literature values.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1061-1070 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Proton relaxation measurements have been used to investigate the effects of crosslinking on the segmental motion in cis-1,4-polybutadiene samples. The temperature dependence of proton spin-lattice relaxation time T1 and spin-spin relaxation time T2 at 60 and 24.3 MHz are reported in cis-1,4-polybutadiene (PB) samples with different crosslink density including uncrosslinked PB and samples with 140, 40, and 14 repeat units between crosslinks. In addition, spin-lattice relaxation times in rotating coordinate frame, T1p, have also been determined. The relaxation data are interpreted in terms of the effects of crosslinks on segmental chain motions. Because of their sensitivity to low-frequency motion, T2 data are of major interest. At temperatures well above the T1 minimum the small T2 temperature dependence resembles solidlike behavior reflecting the nonzero averaging of dipolar interactions due to anisotropic motion of the chain segments between crosslinks. The magnitude of T2 at 60°C is found to be proportional to the average mass between crosslinks.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1079-1087 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The molecular weight distribution of fractionated and unfractionated polystyrene samples has been determined by temperature drop turbidimetry, in which polymer is precipitated from dilute solutions in cyclohexanol by progressively cooling from 388 to 310 K. Estimates of the molecular weight averages and the polydispersities, obtained by calibration of the temperature of initial onset of precipitation, Ti, and the weight-average molecular weight were low, but could be substantially improved by correcting for concentration changes during precipitation. An empirical procedure correlating the breadth of turbidity-temperature curves to the logarithm of the polydispersity, as measured by gel permeation chromatography, appeared to be a simpler method of characterizing the polymer samples and as accurate as the computational methods above.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1089-1097 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general solution is presented for the kinetics of an A-A plus B-C step polymerization. B and C are the same type of functional group but with different reactivities (k1 and k2, respectively) toward A groups. The decay of the concentrations of B, C, and A groups and the increase in the degree of polymerization with time are described for various values of the ratio k2/k1.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1099-1104 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyterephthalamides of high molecular weight (ηinh up to 1.9) were obtained by the direct polycondensation reaction of terephthalic acid and aromatic diamines in the presence of poly(ethylene oxide) (PEO) with triphenyl phosphite in a N-methylpyrrolidone (NMP)-pyridine solution that contained lithium chloride. The molecular weights of the polymers produced varied with the amount and molecular weight of PEO, which showed maximum values when PEO with a molecular weight of 2.0 × 104-5.0 × 105 was used in a concentration of about 0.5 wt % in the solvent. The polycondensation reaction was significantly affected by the level of pyridine in a mixed solvent of NMP and pyridine and by the concentration of the lithium chloride added.
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1451-1473 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolymers of styrene with vinylphenyl trifluoromethyl carbinol, p-vinylphenyl trifluoromethyl carbinol, vinylphenyl hexafluorodimethyl carbinol, and p-vinylphenol are conditionally compatible with poly(ethylene oxide), depending on their composition and blending ratios, whereas copolymers of styrene and vinylphenyl methyl carbinol are much less compatible with poly(ethylene oxide), as determined by Tg criteria and differential scanning calorimetry. The crystallinity of poly(ethylene oxide) is changed in the copolymer/poly(ethylene oxide) blends, as indicated by depressions of the poly(ethylene oxide) melting point. Hydrogen-bond formation has been studied in two selected blends by infrared (IR) spectroscopy. Hydrogen bonding dissociation and reassociation as a function of temperature are reported. The conformation changes of poly(ethylene oxide) in the blends, the interaction between copolymer and poly(ethylene oxide) as well as in the reference blend, polystyrene/poly(ethylene oxide), are also investigated.
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1475-1493 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The determination of the free radical distribution in the preflame and flame zones of a burning polymer (polypropylene) by ESR leads to the conclusion that in all phases of the burning polymer an exothermic reaction zone encloses an oxygen-free pyrolytic zone. Whereas in the molten preflame zone (250-350°C) the polymer decomposes to oligomers, dimers, monomers, and the relevant free radicals or biradicals, in the gaseous flame zone the heat transport from the hot outer surface into the surrounding pyrolytic zone leads (with an increasing temperature gradient) to a progressive formation of thermodynamically more stable decomposition products. The CH. radicals generated at 400-800°C, after rapid cooling, yield polyaromaties with delocalized free electrons and the atomized carbon and its dimers at 800-1200°C, after cooling, yield graphite sheets with localized free electrons in its defects. Free radicals and paramagnetic species are trapped (a) in the gaseous pyrolytic products of heated polymers on the surface of a rotating cryostat, (b) in burning polymer drops by quenching in liquid nitrogen, and (c) in different zones of a burning diffuse flame. The superimposed ESR signals of the paramagnetic products are then qualitatively and quantitatively analyzed.
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1509-1515 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Well-defined low-molecular-weight polystyrene was grafted onto cellulose acetate in a homogeneous solution. The grafting was performed by esterifying the free hydroxyls in the cellulose acetate (acetyl DS 2.5) with anionically prepared polystyrene having a carboxylic acid group at one end of the chain. The carboxylic acid end group of the polystyrene was activated by either conversion to the corresponding acid chloride, or by reaction with trifluoroacetic anhydride. Pyridine and the more active 4-dimethylaminopyridine were used as catalysts in the esterifications. The polystyrene contents of the copolymers varied between 10 and 80% and the molecular weights of the polystyrene grafts were 2500, 12,100 and 17,100 (M̄w/M̄n = 1.1).
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1495-1508 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Qualitative and quantitative free radical transformations between polypropylene alkyl radicals, oxygen, and brominated flame retardants in the molten and gaseous phases of thermally treated samples are described. By ESR technique it has been proved that, depending on the applied pressure during pyrolysis, highly reactive peroxy radicals or less reactive radicals of the retardant are formed. For flame-retarded samples, compared with polypropylene without additives, the concentration of the primary alkyl radicals transferred from the molten to the gaseous phase is reduced by two orders of magnitude (from 7 × 1014 to 7 × 1012 spins/0.02 g), whereas the limiting oxygen index [LOI] is raised from 17-18% to 25-26%. The great variety of physical and chemical processes proceeding in molten polymer in the preflame zone and burning gaseous phase calls for use of different retardant types with a programmed release of Br and HBr with the temperature increase. The chain oxidation of the “fuel,” a product of the endothermic decomposition of polymer, determines the temperature of self-ignition according to the number of initiating alkyl and allyl radicals formed per unit time; the [LOI] index depends more on the length of the kinetic chain of propagation reactions in the stationary process of oxidation at a given pressure.
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1517-1524 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The aqueous polymerization of methacrylamide (I) initiated by KBrO3-thioglycolic acid (TGA) has been studied at 30 ± 0.2°C in nitrogen. The rate is given by K[M]1.19 [thioglycolic acid]1 [KBrO3]0.53 for 10-15% conversion. Activation energy was found to be 53.96 kJ/mole (12.92 kcal/mole) in the investigated range of temperature 30-45°C. The role of addition of a series of aliphatic alcohols and some salts was also determined. The kinetics of polymerization was followed iodometrically.
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1533-1538 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: β-Pinene and epichlorohydrin (ECH) have been copolymerized cationically using BF3(C2H5)2O and SnCl4 as catalysts. Polymerizations were carried out at -80°C in methylenechloride. Monomer reactivity ratios were determined in both catalysts which were r1(ECH) = 1.06 ± 0.15 and r2 (β-pinene) = 0.32 ± 0.08 in BF3(C2H5)2O and r1(ECH) = 0.33 ± 0.11 and r2(β-pinene) = 2.03 ± 0.44 in SnCl4. Copolymers of different composition were soluble in acetone and insoluble in methanol. This characteristic was taken to indicate that the polymeric products were real copolymers and not a mixture of two homopolymers of epichlorohydrin and β-pinene.
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  • 64
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1297-1323 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A mathematical formulation is given which describes the evolution of the number distribution of the molecular weight (MWD) of linear polymer chains that grow in emulsion polymerization systems. The resulting set of coupled ordinary differential equations takes into account the microscopic events of free radical entry, exit, chain annihilation, bimolecular termination (by combination and disproportionation), and chain transfer in a mono- or polydisperse system. Simple analytic solutions are presented for systems in which the number of particles, as well as the average number of free radicals per particle, is constant and in which the rate coefficients are size independent. These solutions indicate that compartmentalization of the free radicals in the latex particles results in a significant increase in the polydispersity of the polymer produced by emulsion polymerization, compared with that in bulk systems. The theory shows that significant mechanistic information may be obtained from experimental MWDs and that, in principle, experimental conditions may be prescribed to grow a desired MWD. The MWDs are presented in a novel manner that facilitates the comparison of theory with experiment.
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  • 65
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1325-1337 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radiation-induced terpolymerizations of methyl α,β,β-trifluoroacrylate (MTFA) with tetrafluoroethylene (TFE) and α-olefins, such as ethylene, propylene, and isobutylene, were carried out in bulk at 25°C for the purpose of controlling the content of ester group in the MTFA-α-olefin alternating copolymers. These monomers polymerized to form alternating terpolymers which contained 50 mole % α-olefin in a wide range of monomer composition. The content of MTFA, namely, the ester group in polymer, can be varied without destruction of the alternating structures between fluoroolefins (MTFA, TFE) and α-olefin by changing the MTFA/TFE ratio in the monomer mixture. The relative reactivities of MTFA and TFE in the terpolymerization were discussed according to kinetic treatments by free propagating and complex mechanisms. The relation between the MTFA/TFE ratio in the monomer mixture and that in terpolymer was explained favourbly by the complex mechanism. It was also concluded that the relative reactivity of MTFA is larger than that of TFE in the terpolymerizations.
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  • 66
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    Topics: Chemistry and Pharmacology
    Notes: Sequential gas-liquid chromotographic analysis of the reaction mixture throughout a copolymerization reaction in conjuction with the improved curve-fitting I (integrated form) method, which accounts for measurements errors in both variables, allows accurate estimation of the monomer reactivity ratios. In this article an alternative method is presented for estimating r values in copolymerization with linear regression only, which is especially suited to cases in which one or two of the r values is close to 1. In these cases the improved curve-fitting I method tends to converge slowly because of the numerical instability of the integrated copolymerization equation. The use of the new method is illustrated for the estimation of the r values for ethylene and vinyl acatate in benzene at 35 kg/cm2 and 62°C. The linear regression method was also tried on other copolymerizations and the results are compared with those obtained from the improved curve-fitting I method. The limits of the applicability of the linear regression method were determined by simulated sequential sampling experiments. It appears that the new method is applicable when the product of the r values is between 0.001 and 2, provided both monomer conversions are large enough compared with the measurements error.
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  • 67
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1339-1346 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Investigations were performed on acetone and benzene-sensitized degradation of triethylene glycol (TEG), polyethylene glycol 400 (PEG 400), and polyethylene glycol 4000 (PEG 4000) in aqueous solutions exposed to irradiation at λ = 254 nm and λ ∼ 313 nm. The systems investigated were exposed at 20°C (±1°C) in both deaerated and undeaerated solutions. The course of the photosensitized degradation was examined viscosimetrically. The determined quantum yield (φ) of chain scission decreases distinctly as the molecular weight of the polymer rises, irrespective of the wavelength of the light absorbed and deaeration of system exposed.
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  • 68
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1359-1366 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Small-angle x-ray scattering methods were applied to calculate macromolecular parameters like specific inner surface (O/V), length of coherence (lc), and the percentage of air present in agave hybrid, treating it as a densely packed colloidal system belonging to a general micelle system. The parameters were equal to O/V = 8.50 × 10-6 Å-1, lc = 150 Å, and the percentage of air = 0.03. The Kratky camera with latest design was used for the experimental measurement. Because the sample agave ybrid is a natural fiber and a highly oriented system that is celluosic in character, the theories of Kratky and Porod have been used to evaluate these parameters.
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  • 69
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1367-1373 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown that the induced Cotton effects in the visible region of the absorption bands of acridine orange in the presence of a nonstereoregular α-carboxylic polysulfonamide (PLL) can be attributed to stacked bound dye molecules, irrespective of the conformation of the polymer. The existence of an ordered structure seems to be unnecessary for such an induction.
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  • 70
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1621-1634 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation dodecane-block-poly[ethylenimine-graft-4(5)-methylimidazole] copolymers and related model compounds has been described and such polymers have been described and such polymers have been demonstrated to be efficient catalysts for the hydrolysis of activated phenyl esters in aqueous solutions. Polymeric catalysts that contain isolated apolar blocks exhibited enhanced catalytic activity for the hydrolysis of the p-nitrophenyl esters of acetate and butyrate compared with polymer model compounds. This rate enhancement was atributed to the apolar binding of substrate within the apolar polymer regime. Twenty-to 100-fold increases in the second-order rate constants were observed for the hydrolysis of the longer-chain p-nitrophenyl esters. This is indicative of a significant hydrophobic interaction. The contribution of the apolar block to the hydrophobic interaction was masked in the hydrolysis of the p-nitrophenyl caproate and p-nitrophenyl laurate substrates. In both instances the dominant contribution to the hydrophobic interactions was ascribed to a substrate-imidazole intermediate rather than the apolar block of the catalyst. The pH-rate profiles for the hydrolysis of p-nitrophenyl esters by the various catalysts indicated an absence of any cooperative interactions between imidazole residues or amine groups.
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1679-1687 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The primary fragmentation mechanisms in the thermal decomposition of polyurethanes were studied in detail by direct pyrolysis into the mass spectrometer. The remarkable difference in the thermal stability of the two totally aromatic polyurethanes I and II (Fig. 1) reflects their different decomposition pathways. In fact, polymer I undergoes a depolycondensation process that yields diiscyanate and dialcohol as primary thermal fragments. The thermal decomposition of polymer II proceeds instead via the formation of a cyclic compound that has been isolated and characterized. In contrast, open-chain fragments are generated in the thermal decomposition of the partially aliphatic polymer III.
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  • 72
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1387-1397 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The phenanthrenechromium dicarbonyl moiety was anchored by a photosubstitution reaction onto commercial resins substituted by diphenylphosphine groups. From scanning electron microscope photographs it was found that, whereas the chloromethylation reaction proceeded homogeneously throughout the polymer beads, the phosphination and photochemical reactions behaved differently, depending on the macrostructure and the morphology of the polymer beads. Large pore size dimensions (1300 Å) allowed the reagents (phosphine and chromium complex) to react throughout the polymer beads, whereas small pore sizes (〈 50 Å) permitted penetration of the reagent only to a limited extent.
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  • 73
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1721-1732 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This investigation deals with the nature and relative abundance of stable radicals formed by gamma-irradiation of wheat starch at room temperature. Additions of equal weights of water, methanol, and ethanol were equally effective in reducing the content of stable radicals in starch which contained about 12% water before the additions. When, however, the starting material was dried starch with 2.9% initial water content additional water and methanol were better radical scavengers than ethanol. This difference is attributed to the superior ability of water and methanol to permeate the starch structure. Superficially different ESR spectra were obtained in products made by irradiating starch and starch that contained added water or methanol. Computer simulation of these spectra showed that they could be matched by superposition of the spectra of the same four component radicals, with some adjustments of relative intensities and peak widths. The structures of these radicals have been dedueed from the spectral assignments and relative effects of the three solvents used on the intensities of the respective ESR spectra.
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1745-1755 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Novel aromatic hetero polymers, polybenzoylenebenzimidazoquinazolines, were prepared. These polymers were synthesized by the polymerization of bis-o-aminophenylbenzimidazoles with aromatic tetracarboxylic dianhydrides in organic solvents, followed by cyclocondensation of the polyamic acids in polyphosphoric acid. In the resulting polymers the o-phenylenediamine component behaved trifuntionally and the connecting groups were tricyclic fused rings that contained seven-membered rings. These polymers some of which has a ladder-type structure, exhibited excellent thermal properties.
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  • 75
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1781-1793 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: S(-) and R(+) enantiomers of α-methyl-α-ethyl-β-propiolactone (MEEPL) were prepared in an eight-step synthesis with respective optical purities of 99 and 97% determined by 1H-NMR (250 MHz) spectroscopy. Polymers (PMEPL) of different enatiomeric compositions were prepared with an anionic-type initiator. Substantial differences in physical properties were observed between the racemic and optically pure polymers; for example, the melting point of the latter is 42°C higher than that of the former. Chiroptical properties of PMEPLs are reported. The 13C-NMR (100.62 MHz) spectra of the polymers indicated that the distribution of configurational units in the macromolecular chain is random.
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  • 76
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    Keywords: Physics ; Polymer and Materials Science
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  • 77
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1433-1446 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preparation and optical properties of linear polyethylenimine (PEI) containing L-(-)-N-[(-)-2-(thymin-1-yl) propionyl] prolyl group as grafting pendant, [P-(-)Pro-(-)T], and its related monomer and dimer model compounds are described. Hypochromic effects and circular dichroism of these compounds were compared with those of PEI containing (-)-2-(thymin-1-yl) propionyl group as grafting pendant, [P-(-)T], which has no L-proline ring as a spacing group. P-(-)Pro-(-)T showed no exciton coupling of B2u π-π* transition although it showed large hypochromicity in neutral aqueous solution, implying that the stacking of the bases has no screw sense.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1459-1469 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electrochemical and chemical polymerization of acrylamide (AA) has been studied. The electrolysis of the monomer in N,N-dimethylformamide (DMF) containing (C4H9)4NClO4 as the supporting electrolyte leads to polymer formation in both anode and cathode compartments. The cathodic polymer dissolves in the reaction mixture and the anodic polymer precipitates during the course of polymerization. A plausible mechanism for the anodic and cathodic initiation reaction has been given. The chemical polymerization of acrylamide that has been initiated by HClO4 is analogous to its anodic polymerization. The polymer yield increases with an increase in concentration of the monomer and HClO4. Raising the reaction temperature also enhances the polymerization rate. The overall apparent activation energy of the polymerization was determined to be ca. 19 kcal/mole. The copolymerization of acrylamide was carried out with methyl methacrylate (MMA) in a solution of HClO4 in DMF. The reactivity ratios are r1 (AA) = 0.25 and r2 = 2.50. The polymerization with HClO4 appears to be by a free radical mechanism. When the polymerization of acrylamide is carried out with HClO4 in H2O, a crosslinked water-insoluble gel formation takes place.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1447-1458 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Graft copolymerization of methyl methacrylate (MMA) was carried out on both defatted and bleached jute fibers using ceric ammonium sulfate (CAS) as the initiator. In order to obtain the optimum condition for grafting, the effects of initiator concentrations, temperature, time of reaction, lignin content of jute, and the monomer concentration were studied. The maximum percent grafting and grafting efficiency were found to be 132% and 0.71, respectively. Kinetic studies showed that at 0.03M CAS, the reaction appeared to obey the second-order process. The activation energies were found to be 7.74 and 5.12 kcal/mole for defatted (lignin content, 15.7%) and chlorite-bleached jute (lignin content 10%), respectively. The activation energies of graft copolymerization of MMA onto jute fiber are compared with the energies of activation of graft copolymerization of acrylonitrile (AN).
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1483-1488 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Simultaneous HCl evolution and spin-generation measurements were made on poly(vinyl chloride) (PVC) samples containing stabilizers of the type Rx Sn Y4-x. It was found that tetrabutyltin and tributyltin laurate were better stabilizers than dibutyltin dilaurate. On the basis of the results, a mechanism for the stabilization of PVC by this class of compounds is proposed.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1471-1481 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Work on the evolution of HCN from nylon 66 was extended to temperatures from ca. 300 to 695°C. Below ca. 300°C the evolution of HCN is governed by chemical decomposition, and above 300°C the evolution is controlled by diffusion. Above 530°C oxidation of HCN becomes noticeable and ignition occurs at 590°C. The rate constants for all of the temperature ranges and for the oxidation of HCN are given in terms of Arrhenius equations. The activation energy for the oxidation of HCN before ignition (590°C) is reached is 47 kcal/mole, and beyond this point, the oxidation is controlled by diffusion. The rate constants increase linearly with oxygen concentration as long as HCN oxidation is negligible; however, they pass through maxima if HCN oxidation is appreciable (some HCN is evolved even in the absence of oxygen). A new flash degradation apparatus has been constructed for these high-temperature ranges and a degradation mechanism has been proposed which is in satisfactory agreement with the experimental results.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1499-1509 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of crotonaldehyde (CA) with ethyl aluminum chlorides have been examined using a titration technique at low temperature. The titrations were followed by 1H-NMR spectroscopy. Evidence for complexes of the type (Et2AlCl)2CA and (Et2AlCl-CA)2 has been obtained. Ethyl aluminum sesquichloride undergoes sequential addition of CA to the EtAlCl2 moiety, to the Et2AlCl moiety, and again to the EtAlCl2 moiety. Ethyl aluminum dichloride undergoes ligand redistribution, alternately disproportionating and reproportionating, the ultimate product being EtAlCl2-CA2.
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    Topics: Chemistry and Pharmacology
    Notes: Acetal additions to β-substituted vinyl ethers having a variety of substituents (alkenyl ethers) were stereochemically investigated as model reactions for their cationic polymerization. The reactions catalyzed by BF3O(C2H5)2 in CH2Cl2 at O°C gave 1:1 adducts, the steric structure of which was determined by means of 13C-NMR spectroscopy. trans-Alkenyl ethers always gave adducts with a single structure stereospecifically, indicating that the intermediate carbocation attacks a trans-alkenyl ether from a definite direction independent of the bulkiness of substituents. On the other hand, cis-alkenyl ethers formed adducts with two steric structures, and the direction of cation addition was found to depend on the bulkiness of the alkoxy group involved. The above trends were in agreement with the results for poly(alkenyl ether)s and allowed detailed discussion of the stereochemistry of the propagation processes in alkenyl ether polymerizations.
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1511-1521 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New processable polyaromatic ether-keto-sulfones were prepared from 2,2′-diiododiphenyl-4,4′-dicarbonyl dichloride (I), bis(p-phenoxybenzene)sulfone (V), isophthaloyl chloride (VI), terephthaloyl chloride (VII), and diphenylether (IX) in Friedel-Crafts-type polymerizations. By varying (VI):(VII) ratio and (V):(IX) ratio and by reducing the polymerization time, soluble, processable polymers were obtained. In these polymers, phenylacetylenyl groups were introduced by replacing the iodine. This process led to soluble and curable polymers. Transparent, tough films and fairly flexible glass fiber laminates can readily be prepared. After curing, the polymers were insoluble and showed excellent chemical and thermal resistance. The curing process increased the polymers' softening temperature by ca. 20°C and produced intersting new useful materials for laminates. Processable poly(arylene sulfone)s were prepared from I, V, and diphenylether-4,4′-disulfonylchloride (X) in a Friedel-Crafts-type polymerization. Different monomer ratios and polymerization times were used. Only low-molecular-weight polymers were obtained. The same result was shown by curable polyester formation from I, VI, VII, and 4,4′-sulfonyldiphenol (XI) in an interfacial polycondensation.
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1985-1994 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cationic polymerization of N-tert-butyl aziridine (TBA) can be conducted in such a way that the rate of termination is much slower than the rate of propagation, thus permitting preparation of a corresponding polymer which is “temporarily living”. Reactions of N-methyl-N-tert-butyl aziridinium triflate (which is the model for the active species of the living polymer) with different nucleophiles show that, at room temperature, the aziridinium ring reacts almost instantaneously with nucleophiles to form the corresponding ring-opened product. Analogous reactions with the aziridinium end group of living poly-TBA lead to polymers with varying end groups such as hydroxy, ester, primary, secondary or tertiary amino, halogen, and others. End group analysis by means of 360-MHz 1H-NMR nuclear magnetic resonance spectroscopy showed that the concentration of the end groups was in all cases equal to the concentration of the methyl head group, originating form the initiation reaction, if the terminating nucleophile was added five minutes after initiation (at 15°C). Under these conditions the polymerization is quantitative for initiator concentrations down to 0.01 mol L-1.
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2017-2026 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A low temperature solution condensation method with pyridine as acceptor-catalytic reagent was applied to the synthesis of polyarylates from carbazole and bisphenol A/phenolphthalein. The polyarylates were classified with respect to their structure, thermal stability, and dielectric behavior.
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2027-2039 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polystyrene with random long chain branches has been difficult to prepare. A new approach using small amounts of chain-transferring monomers to copolymerize with styrene free radically was examined in this work. Of the several comonomers examined, vinylbenzylthiol yielded polystyrene with branched structure. But because of the high chain trnsfer constant, the branches occurred mainly in the low-molecular-weight end of the distribution. As a side interest, vinylbenzylthiol was found to be an effective agent for the broadening of molecular weight distribution.
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2053-2063 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ozonolysis of spruce periodate and cuoxam lignins and protolignin in spruce wood has been studied in 45% aqueous acetic acid at room temperature. Stirring affected the rate of reaction and a tentative explanation is given. Degradation followed first-order kinetics characterized by a rate constant K with values of 6.96 × 10-4s-1 for periodate lignin, 5.10 × 10-4s-1 for cuoxam lignin, and 5.09 × 10-4s-1 for protolignin in spruce wood. The similarity of the rate constants shows (1) that periodate and cuoxam lignins are good models for wood lignin and (2) that the carbohydrate matrix has an insignificant effect on the rate of delignification of the protolignin by ozone. The average rate of ozone consumption per C9 unit for periodate lignin was determined as 0.12 mol/min and 0.08 mol/min for cuoxam lignin. The implications of the various results are discussed.
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  • 89
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2065-2078 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The molecular weights and molecular weight distributions of the alkali-soluble degradation products from the ozonolysis of spruce periodate and cuoxam lignins and spruce protolignin have been studied by gel permeation chromatography and ultracentrifugation. The bimodal distribution previously reported for soluble lignins was found to be an artifact; the correct distribution has one broad lowmolecular-weight maximum, with a long tail extending toward the high-molecular-weight end of the distribution. Weight-average molecuar weights of the alkali-soluble degradation products, obtained by sedimentation equilibrium measurements, increased with time of ozonization up to about 15 min. Beyond this time fragmentation of the partly degraded products results in a decrease in molecular weight. Lignin degradation followed the pattern expected of a three-dimensional, infinite-network polymer gel undergoing breakdown. Based on the molecular weights and the molecular weight distributions, a random stepwise mechanism is suggested as the mode of lignin degradation by ozone.
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  • 90
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2103-2104 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 91
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2105-2109 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
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  • 92
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2115-2118 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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  • 93
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2123-2125 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 94
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2161-2165 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cyclopolycondensation of linear bis-β-diketones with aromatic dihydrazines in dimethyl sulfoxide at 100-150°C produced a series of aromatic polypyrazoles with inherent viscosities up to 0.6 dL/g. All the polymers were highly soluble in a wide range of solvents, which included tetrahydrofuran and chloroform. The polypyrazoles showed excellent thermal stability with 10% weight loss at 410-490°C in air and nitrogen atmosphere.
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  • 95
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2167-2174 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New polythioesters by interfacial polycondensation of 4,4′-di(mercaptomethyl) benzophenone with oxalyl, succinyl, adipoyl, suberoyl, and sebacoyl chlorides were obtained. To determine the optimal conditions for interfacial polycondensation the influence of the following factors on yield and value of reduced viscosity were studied: type of organic phase, the quantitative ratio of aqueous and organic phase, concentration of hydrogen chloride acceptor, molar ratio of reagents, temperature of reaction, rate of acid chloride addition, and contribution of catalyst and emulsifier. A thorough examination was carried out only for polycondensation of dithiol with adipoly and sebacoyl chlorides. The structure of all polythioesters obtained under the model conditions was determined by elementary analysis and infrared spectra. Initial decomposition and initial intensive decomposition temperature were defined from the curves of thermogravimetric analysis. Some mechanical and electrical properties of the polythioesters obtained from 4,4′-di(mercaptomethyl)benzophenone and adipoyl and sebacoyl chlorides were determined. The molecular weight was not measured because of the low solubility of the obtained polythioesters.
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  • 96
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2185-2194 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of cyclohexene oxide was investigated with a new catalyst system of Al(acac)3- silanol compounds. Catalyst activity varied with the ratio of silanol/Al(acac)3 and the structure of silanol compounds. Catalyst deactivation appeared to be caused by self-condensation of silanol and the addition of silanol to the epoxy ring. Polymer structure was investigated by 13C-NMR spectroscopy and x-ray diffraction. The mechanism of the polymerization appears to be cationic.
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  • 97
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2215-2228 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New graft copolymers were synthesized by grafting hydroxyethyl methacrylate and hydroxpropyl methacrylate on poly(vinyl alcohol) in aqueous solution with Ce+4ions as initiator. The dependence of the percentage of grafting and monomer conversion on the concentration of the monomer, on the concentration of the initiator, on the total concentration of the reactants, and on temperature and duration of the reaction were investigated. Some basic properties of the graft copolymers and some preliminary permeation measurements of water vapors through films, made from these copolymers, are also reported.
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  • 98
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2243-2253 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The amine catalyzed isomerization of itaconic to citraconic anhydride has been investigated. Studies show that the rate of isomerization is dependent on the base strength and solvent media. Triethylamine causes complete isomerization within 5 min at room temperature in acetone or chloroform solvent, whereas aromatic tertiary amines such as pyridine and N,N-dimethylaniline require time perods as long as 23h at room temperature for almost complete isomerization. In the presence of aniline no isomerization occures even under acetone reflux conditions over a 24 h period. For the preparation of citraconamic acids from itaconic anhydrides and aliphatic diamines nuclear magnetic resonance and infrared spectroscopic evidence is presented to support the reaction path of initial isomerization of itaconic anhydride to citraconic anhydride followed by amine attack on the anhydride to form the corresponding cis-citraconamic acids. The mechanism of isomerization of itaconic to citraconic acids is proposed.
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  • 99
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    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2269-2274 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A rapid dechlorination method of N-chloro poly(hexamethylene adipamide) and N-chloro poly(ε-caprolactam) to the corresponding polyamides was studied. This method can be used for molecular weight determinations of N-chloro polyamides by viscosimetric measurements. The dechlorination was achieved in formic acid solution by the reaction of N-chloro polyamides with trialkyl phosphites. The reaction was exothermic and vigorous and was applied to a series of products of various degrees of N-chlorination covering the range of 0-100%. No N - Cl was detected by iodimetric titration of the dechlorination products. The dechlorination of N-chloro polyamides was demonstrated by infrared (IR) spectroscopy. No significant molecular weight reduction except that taking place in the N-chlorination reaction of poly(hexamethylene adipamide) was observed.
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  • 100
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    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 1633-1634 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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