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  • 1980-1984  (2,989)
  • 1970-1974  (2,972)
  • 1830-1839
  • Physics  (5,204)
  • Electron microscopy  (757)
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Year
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  • 101
    Electronic Resource
    Electronic Resource
    New telechelic polymers and sequential copolymers by polyfunctional initiator-transfer agents (inifers). XLI. Kinetic and reactivity studies on sterically hindered inifers (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2685-2697 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of chain transfer to the bifunctional initiating and transfer agents (binifers) 1,4-di(2-chloro-2-propyl)benzene (p-DCC), 1,3-di(2-chloro-2-propyl)-5-tert-butylbenzene (m-tBuDCC), and 1,3-di(2-chloro-2-propyl)-4,6-dimethylbenzene (m-DMeDCC) in the polymerization of isobutylene has been investigated. Chain transfer to monomer was shown to be absent up to -20°C in CH3Cl/n-hexane and CH2Cl2/n-hexane mixtures using the m-tBuDCC/BCl3 binifer system. Chain transfer constants (Ci) to m-tBuDCC and kt/kp ratios determined in the range from -30°C to -80°C in CH3Cl/n-hexane mixtures and pure CH3Cl solvent are reported, and the activation energy differences Etr,l - Ep and Et - Ep were calculated. Chain transfer constants to p-DCC and m-DMeDCC were determined by the use of pure CH3Cl diluent at -50°C. The chain transfer reactivity of five different inifers is discussed and compared based on CI values obtained under identical conditions, with special regard to the new, sterically hindered binifer m-DMeDCC of extraordinary reactivity.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221032
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  • 102
    Electronic Resource
    Electronic Resource
    Polyelectrolyte influences on the trans-cis isomerization of sodium m-(4-ethoxyphenylazo)benzene sulfonate (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2945-2952 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Influences of microenvironment of various polyelectrolytes, i.e., ionene polymers and polyamine sulfones, on the photo- and/or thermal isomerization between the trans and cis forms of sodium m-(4-ethoxyphenylazo)benzene sulfonate (SEPS) were studied. 6,6-Ionene demonstrated larger enhancing effect on the cis-trans thermal isomerization than 3,3-ionene, which indicated that the micropolarity or the pH around the polymer is important. In the Arrhenius plots for both photo- and thermal isomerizations, deviations from the linearity were observed. In the former case, a sharp bend and the negative apparent activation energy were obtained at the high temperature. Furthermore, they were sensitively affected by the polyelectrolytes.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221118
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  • 103
    Electronic Resource
    Electronic Resource
    Functionalization of polymeric organolithium compounds. Oxidation (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2993-3000 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of poly(styryl)lithium with molecular oxygen was investigated in the solid state (with and without N,N,N′, N′-tetramethylethylenediamine) in benzene (with and without N,N,N′, N′-tetramethylethylenediamine) and in benzene/tetrahydrofuran (THF) solutions. The oxidation products included the corresponding polystyrene dimer [(PS)2], the dimeric poly(styrene) peroxide (PSO2PS), poly(styrene) hydroperoxide (PSO2H), and the hydroxyl-terminated polymer (PSOH). The hithertofore unreported macroperoxide (PSO2PS) accounts for approximately 50% of the dimeric product obtained from poly(styryl)lithium oxidations in the presence of Lewis bases. The total amount of peroxide products was determined by iodometric titration in the presence of a phase-transfer catalyst, dicyclohexyl-18-crown-6. On the basis of the effect of polar additives on the amount of dimeric products, it is concluded that dimer formation in the air termination of polymeric organolithium compounds results from oxidation and not carbonation reactions.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221122
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  • 104
    Electronic Resource
    Electronic Resource
    The kinetics of oxidative coupling of 2,6-dimethylphenol with a copper-diamine catalyst system (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3203-3215 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction rate measurements show that a Michaelis-Menten model proposed earlier is inadequate to describe the full course of the polymerization of 2,6-dimethylphenol to poly(2,6-dimethyl-1,4-phenylene oxide). Modification of this model to include the effects of catalyst deactivation during the reaction and difference in reactivity between the monomer and other oligomers resulted in much greater accuracy. The kinetic constants in the modified model were influenced by reaction temperature, system composition, and method of catalyst component addition.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221139
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  • 105
    Electronic Resource
    Electronic Resource
    Isothermal pyrolysis of cellulose untreated and treated with some flame-retardants (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3071-3089 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Linter cellulose, untreated and treated with boric acid, ammonium sulfamate, and guanidine sulfamate, was heated iosthermally in an imaging furnace thermal balance under a flow of helium gas to obtain kinetic parameters of the weight loss and changes in the elemental content and infrared (IR) spectra during pyrolysis. The weight, carbon, hydrogen, and oxygen losses of the untreated cellulose obey a zeroth-order reaction at an early stage and a first-order reaction at a later stage. The Arrhenius parameters for the weight and elemental losses are in agreement for both reactions. The activation energy and preexponential factor of the first-order weight loss are 185 kJ/mol and 2.0 × 1013 s-1, respectively. The carbon, hydrogen, and oxygen losses of the samples treated with boric acid and guanidine sulfamate also obey a first-order reaction at a later stage of pyrolysis. The results of the elemental and IR spectral analyses suggest that the zeroth- and first-order reactions are caused mainly by the production of levoglucosan and that an initial rapid step, especially for the treated samples, is contributed by dehydration.
    Additional Material: 21 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221128
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  • 106
    Electronic Resource
    Electronic Resource
    Liquid crystal polymers. XVIII. Comparison of the properties of aromatic polyesters with different mesogenic units and a common flexible spacer (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3189-3201 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four closely related polyesters, with aromatic ester triads and decamethylene spacers, were prepared and characterized for their thermotropic liquid crystalline properties. Two of the polymers, which were based on linear biphenols, formed stable nematic phases, whereas one of the two based on nonlinear biphenols formed a poorly defined nematic phase; the other was not liquid crystalline. Several polymerization reactions and methods were evaluated and structure-property relationships of the polymers are discussed. The concept of “degree of liquid crystallinity” for polymers with poorly defined thermotropic behavior is considered.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221138
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  • 107
    Electronic Resource
    Electronic Resource
    Kinetics of emulsion polymerization of methyl methacrylate (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3225-3253 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the emulsion polymerization of methyl methacrylate at 50°C have been studied in seeded systems using both chemical initiation and γ-radiolysis initiation. Both steady-state rates and (for γ-radiolysis) the relaxation from the steady state were observed. The average number of free radicals per particle was quite high (e.g., ∼0.7 for 10-3 mol dm-3 S2O28 initiator). The data are quantitatively interpreted using a generalized Smith-Ewart-Harkins model, allowing for free radical entry, exit, biomolecular termination within the latex particles, and aqueous phase hetero-termination and re-entry. From this treatment, there results (i) the dependence of the termination rate coefficient (kt) on the weight fraction of polymer (wp), (ii) lower bounds for the dependence of the entry rate coefficient on initiator concentration, and (iii) the conclusion that most exited free radicals undergo subsequent re-entry into particles rather than hetero-termination. The results for kt(wp) are consistent with diffusion control at temperatures below the glass transition point. Comparisons are presented of the behavior of methyl methacrylate, butyl methacrylate, and styrene in emulsion polymerization systems.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221141
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  • 108
    Electronic Resource
    Electronic Resource
    Mechanism of the thickening reaction of polyester resins: Study on models (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3309-3318 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thickening reaction of polyester resins is investigated using model compounds, diesters or polyesters of 1,2-propanediol and phthalic acid with dihydroxy or dicarboxy end groups. Soluble magnesium acetylacetonate was found to be an effective thickener, and for the first time it was possible to study a thickening reaction in homogeneous media (THF solutions). The results are compared with those obtained with MgO. The proposed mechanism supposes that the central step consists of the formation and the aggregation of magnesium carboxylates in ionic areas, with entanglement of attached polyester chains. This fits our experimental results better than the hypothesis of coordination of magnesium carboxylates by ester or hydroxyl groups of the chains2-6 or than the hypothesis of the formation of linear high molecular weight compounds.7-9
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221146
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  • 109
    Electronic Resource
    Electronic Resource
    Polymerization of allyldimethyldodecylammonium bromide in micellar and isotropic media (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3383-3391 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To study the effect of micellar aggregation upon polymerization and polymer products, the polymerization of the micelle forming monomer allyldimethyldodecylammonium bromide (I) was investigated under both micellar and isotropic conditions. NMR spectroscopy and fluorescence quenching were employed to elucidate the structural characteristics and molecular weight of the polymer obtained by γ-ray irradiation. It was found that (I) undergoes effective polymerization in the micellar state, producing a polymer which consists of a mixture of head to tail and head to head configurations at the ratio 85/15, and has a mean molecular weight of 11,000 ± 1000 daltons.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221153
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  • 110
    Electronic Resource
    Electronic Resource
    Property relationships in dimer acid-modified copolyesters of poly(1,4-cyclohexylene dimethylene terephthalate) and poly(1,4-cyclohexylene dimethylene 1,4-cyclohexane dicarboxylate) (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 171-183 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dimer acid (D) modified copolyesters based on 1,4-cyclohexane dimethanol (CHDM) and either terephthalic acid (T) or trans-1,4-cyclohexane dicarboxylic acid (C) were examined. Both series produced clear, flexible materials with physical properties changing regularly with changing modifier levels. Yield stress, elongation at break, and Young's modulus showed linear correlations of log property versus volume fraction of CHDM-D segments in accord with the logarithmic rule of mixtures. Annealing the CHDM-T-based copolyesters caused little or no change in properties. Annealing the CHDM-C-based copolyesters gave similar results except for a large decrease in the modulus - the higher the dimer acid level, the larger the decrease in modulus. The density measurements, the x-ray pattern, and the dynamic mechanical analysis at 110 Hz before and after the annealing treatment supported the hypothesis that the modulus decrease resulted from domain perfection in the copolyester induced by the annealing process. Transmission electron-microscope examination of osmium tetroxide-stained films supported this hypothesis, although initial results were not repeatable.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220117
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  • 111
    Electronic Resource
    Electronic Resource
    Studies on some newer polyamides (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3599-3602 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221172
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  • 112
    Electronic Resource
    Electronic Resource
    DSC studies of phase transitions in poly(diethylsiloxane) (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3617-3632 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The differential scanning calorimetry studies have shown that high-molecular linear poly(diethylsiloxane) can exist in two high-temperature polymorphs which melt at 280 and 290 K. The heats of fusion of the high-temperature polymorphs are 17 and 21 J/g, respectively. Each of the high-temperature forms arises from the corresponding low-temperature form the corresponding low-temperature form when the polymer is heated: the first at 214 K (transition heat is 28 J/g) and the second at 206 K (transition heat is 26 J/g). The mesophase formed from the molten high-temperature crystalline phases melts in a rather broad temperature range of 290 to 327 K, and the heat of this transition is 2.7 J/g. Crystallization of poly(diethylsiloxane) from the mesomorphic and the supercooled amorphous state is different. In the first case, apparently, the whole mesophase is converted to the crystalline phase and the samples have a crystallinity near 1. In the second case the crystallinity is only ca. 0.3. The temperature range in which the mesophase melts depends on the molecular weight of the polymer, presence of crosslinks and the conditions under which it has been formed, e.g., temperature.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221201
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  • 113
    Electronic Resource
    Electronic Resource
    Water-soluble copolymers. IX. Copolymers of acrylamide with N-(1,1-dimethyl-3-oxybutyl)acrylamide and N,N-dimethylacrylamide: Synthesis and characterization (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3633-3647 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymerizations of acrylamide (AM) with N-(1,1-dimethyl-3-oxybutyl)acrylamide (DAAM) and with N,N-dimethylacrylamide (DMAM) have been studied. The values of r1,r2 have been determined to be 0.75 for the AM-DAAM pair and 0.86 for the AM-DMAM pair. The molecular weights of the copolymers were found to decrease with an increase in the feed composition of DAAM or DMAM. The microstructure was predicted for a wide range of feed compositions through a knowledge of reactivity ratios. These model structures are utilized for assessment of structure/dilute solution relationships reported in a subsequent paper in this series.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221202
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  • 114
    Electronic Resource
    Electronic Resource
    Membranes obtained by preirradiation grafting of acrylic acid onto poly(tetrafluoroethylene-perfluorovinyl ether) (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3673-3685 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Some properties of the membranes obtained by preirradiation grafting of acrylic acid onto poly(tetrafluoroethylene-perfluorovinyl ether) copolymer (PFA) films have been investigated. The dimensional change caused by grafting and swelling behavior, water uptake, electrical conductivity, and mechanical properties of the grafted films were found to increase as the grafting proceeds. The influence of the preparation conditions (such as preirradiation dose, monomer concentration, grafting temperature, and film thickness) on those properties was studied. These properties were found to be dependent mainly on the degree of grafting regardless of grafting conditions, except at higher monomer concentration (〉40 wt %). The electric conductivity and mechanical properties for the membranes obtained at higher AAc concentrations were lower than those obtained at lower ones. Analysis by x-ray microscopy of the grafted films revealed that the grafting begins at the part close to the film surface and proceeds into the central part with progressive diffusion of monomer to give finally homogeneous distribution of the electrolytes in the whole bulk of the polymer. The membranes show good electrochemical and mechanical properties which make them acceptable for practical use as cation-exchange membranes.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221205
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  • 115
    Electronic Resource
    Electronic Resource
    Modification of catalysts for propylene polymerization: Alcohols and lewis bases (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3739-3746 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of compounds were examined as modifiers for the high activity supported catalyst TiCl4/MgCl2-AlEt3 for isospecific propylene polymerization. The list included two aromatic acid esters, 21 various Lewis bases, and 12 alcohols. A convenient graphic method is described for comparing the performance of different modifiers by plotting experimental results in coordinates “relative activity-isotactic index” and a kinetic rationale for this evaluation is presented. Aromatic acid esters exhibit much better performance than the bulk of Lewis bases but some sterically demanding aromatic alcohols show behavior show similar to that of the esters.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221211
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  • 116
    Electronic Resource
    Electronic Resource
    Preparation of polysiloxanes from silicic acid. VII. Effects of the degree of esterification and alkyl groups on condensations of silicic acid esters and formation of fibrous silicaPart VI of this series appears in J. Polym. Sci. Polym. Ed., 22, 565 (1984). (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3759-3769 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Silicic acid esters were prepared by the reaction of the silicic acid in tetrahydrofuran with various alcohols such as such as methanol, ethanol, 2-propanol, 1-butanol, 2-methyl-2-propanol and 1-octanol, using an esterification apparatus designed especially to allow the preparation of silicic acid esters from alcohols with low boiling points or appreciable steric hindrance. With the intent of obtaining a spinnable ester solution by condensation of silicic acid esters, the effects of the degree of esterification (DE) and alkyl group on gel time and spinnability are investigated. An increase in the DE and the size of the alkyl group led to an increase in the gel time of the esters. Esters solutions with a good spinnability were prepared from n-butyl and isopropyl esters with DEs of 40-50%. In addition, the gel permeation chromatography of condensing esters with low DEs showed a rapid increase in molecular weight. The results showed that spinnability depended on DE and the ester's alkyl group. Fibers could be formed with length of about 10-100 cm from ethyl, isopropyl, and n-butyl esters with DEs 40-50% and with length of 10 cm from octyl ester with DE 26%.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221213
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  • 117
    Electronic Resource
    Electronic Resource
    Photopolymerization initiated by charge-transfer complex. VI. Photopolymerization of methyl methacrylate with the use of isoquinoline-chlorine charge-transfer complex (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 429-435 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of methyl methacrylate in visible light was studied at 30°C using the isoquino-line-chlorine charge-transfer complex as the photoinitiator. Analyses of kinetic and other data indicate that the polymerization proceeds via a radical mechanism and the termination is initiator dependent. Chain termination via degradative chain (initiator) transfer appears to be significant.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220214
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  • 118
    Electronic Resource
    Electronic Resource
    Thermal and radiation-induced polymerizations of N-tert-butylacrylamide and (N-tert-butylacrylamide)2-ZnCl2 complex (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 453-462 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal and radiation-induced in-source and postirradiation polymerizations of N-tert-butylacrylamide and (N-tert-butylacrylamide)2-ZnCl2 complex of this monomer were studied at various temperatures. In in-source, solid-state polymerizations of monomer and complex the conversion was about 95% at 21°C in about eight days. Their postirradiation polymerizations were also studied in solid state. The conversion-time curves of these two systems show an autoacceleration as in-source polymerization. In both types of polymerization the overall rate of polymerization of complex was higher than that of pure monomer at the same polymerization temperature. In investigations of the thermal polymerization of N-tert-butylacrylamide and ZnCl2-complex it was observed that the ZnCl2-complex system can be polymerized in air in the molten and solid state. The conversion of monomer to polymer reaches limiting values in solid state in about 1 hr. The thermal polymerization of ZnCl2-complex in the molten state was also studied and 100% conversion was obtained in 30 min. The thermal polymerization of pure monomer was studied in vacuum and an appreciable amount of polymer was obtained in the molten state; however, the thermal polymerization of this monomer is negligible in solid state. In this work rates of polymerization for N-tert-butylacrylamide and (N-tert-butylacrylamide)2-ZnCl2 are compared under various experimental conditions and overall activation energies are calculated.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220216
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  • 119
    Electronic Resource
    Electronic Resource
    Ordered heterocyclic copolymers. Polyamide-imides with S-triazine rings (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 503-507 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220220
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  • 120
    Electronic Resource
    Electronic Resource
    Sulfonation chemistry of some small molecule models of EPDM rubbers. II. The structure of intermediate adducts (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3905-3919 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As previously reported, our initial investigation was concerned with the bicyclic olefins, ethylidene norbornane, and dihydrodicyclopentadiene. The former produced a skeletally rearranged γ-sultone and the latter an allylic sulfonic acid. In an attempt to further clarify the mechanisms of the sulfonation of these two models and to extend the study to models of other types of EPDM, we have now examined the sulfonation of several other model olefins. In addition to the bicyclic olefins reported previously, we have studied the sulfonation of monocyclic type II and III olefins and cyclic type I and type II olefins. The results showed that the bicyclic olefins behaved differently from their monocyclic analogs reinforcing earlier speculation as to a synchronous reaction mechanism. Exocyclics gave allylic sulfonic acids while endocyclics produced β-sultones, which is the exact reverse of what was observed for the bicyclic counterparts. Acyclic type II olefins produced “stable” β-sultones, and the influence of the sulfonating reagent on the subsequent chemistry is discussed. Type I olefins, curiously, gave a complex mixture of initial products which tended to rearrange to essentially a single thermodynamic product. The results of the investigation suggest that based on these models, each of the three major types of EPDM should have a different sulfonation mechanism.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221227
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  • 121
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    Tetraalkyl titanium and zirconium metal chloride catalyst systems for ethylene polymerization (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 637-644 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Coordination polymerization of olefins has become an industrially important, yet still poorly understood enterprise. The ethylene polymerization activity of (neophyl)nZrCl4-n shows a twentyfold increase from n = 4 to n = 3 and a further tenfold increase to n = 2. The heterogeneous MR4/TiCl4 catalysts (M = Ti, R = benzyl; M = Zr, R = benzyl, neophyl) have been developed. To explore the breadth of extendability, other metal chlorides (main group and transition metal) were substituted for TiCl4. Indeed, excess AlCl3 or MgCl2 and the MR4 compounds also produced ethylene polymerization catalysts. The inactivity of corresponding (neophyl)4Ti systems is attributed to sterics. The abovementioned catalysts highlight the necessity of alkyl and chloride ligands at the transition metal catalyst centers.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220313
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  • 122
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    Aminopropylcellulose, synthesis and derivatization (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 975-984 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation of 3-aminopropylcellulose from cyanoethylcellulose is readily achieved. Reduction of the cyano groups with borane-dimethyl sulfide in tetrahydrofuran or a borane-tetrahy-drofuran complex proceeds quantitatively in 3 h to a corresponding 3-aminopropylcellulose. The presence of primary amine functions is confirmed by spectroscopy and a positive ninhydrin test; the concentration of amino substituents, as ascertained by titration, ranged from 1.2 to 6.4 meq/g. Because the derivatives are neither soluble nor excessively swollen in water, applications as ion-exchange resins or chromatographic supports can be envisioned. Treatment of 3-aminopropyl-cellulose with acetyl chloride, phenyl isocyanate, or p-toluenesulfonyl isocyanate produced 3-acetamido-, 3-(N′-phenyluredo)-, or 3-(N′-p-toluenesulfonyluredo)-N-propylcellulose. Alkylation with methyl chloride yielded a water-soluble quaternary ammonium salt.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220408
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  • 123
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    Synthesis of aromatic polythioamide-oxothioxoquinazolines from bis(1,3,4-thiadiazoline-5-thione) and aromatic bis-o-amino esters (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1017-1023 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aromatic polythioamide-oxothioxoquinazolines were synthesized by the polycondensation of 2,2′-(m-phenylene)bis-1,3,4-thiadiazoline-5-thione with aromatic bis-o-amino esters. The polymerizations were carried out at 160°C in acidic media such as m-cresol, sulfolane, and polyphosphoric acid to produce polymers with reduced viscosities up to 0.5 dL/g. These polymers were soluble in polar aprotic solvents like N-methyl-2-pyrrolidone and some acidic media including m-cresol. The polythioamide-oxothioxoquinazolines showed relatively good thermal stability with 10% weight loss at 344-394°C in air.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220502
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    Phenothiaphosphine-containing polyamides and polyestersThis work is Part XXIX of Preparation of Phosphorus-Containing Polymers. (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1055-1064 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Phosphorus-containing polyamides and polyesters, which had tricyclic fused rings (phenothia-phosphine rings) in the main chain, were prepared and the properties of the resulting polymers were examined. These polymers were obtained at highly reduced viscosities in satisfactory yields by the polycondensation of 2,8-dichloroformyl-10-phenylphenothiaphosphine 5,5,10-trioxide with aromatic diamines or bisphenols. The polyamides and polyesters were soluble in polar aprotic solvents such as dimethylacetamide and N-methyl-2-pyrrolidone; the polyesters were also soluble in chloroform. The polymers exhibited good heat resistance. The phenothiaphosphine-containing polyamides and polyesters self-extinguished immediately when flame was removed and were highly flame-resistant. The polyester obtained from bisphenol A showed a limiting oxygen index value of 43.5.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220506
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  • 125
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    Ring formation on heating poly(methyl vinyl ether-alt-ammonium maleamate) (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1115-1121 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(methyl vinyl ether-alt-ammonium maleamate), when heated at up to 100°C while removing volatiles, is converted to polymer whose infrared, elemental analysis and Tg are consistent with a structure predominantly that of poly(methyl vinyl ether-alt-maleic anhydride). Maleimide comonomer units are a substantially lesser component. Evidence is presented that a part of the reaction sequence may involve hydrolysis of imide or amide.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220511
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  • 126
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    Functional metal-porphyrazine derivatives and their polymers. VIII. Catalase-like activity of Fe(III)- and Co(II)-2,9,16,23-tetracarboxyphthalocyanine supported on poly(2-vinylpyridine-CO-styrene) (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1309-1318 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition reaction of hydrogen peroxide by Fe(III)- and Co(III)-2,9,16,23-tetracarboxyphthalocyanine supported on poly(2-vinylpyridine-CO-styrene) and the quaternized one, was studied at pH 7.0 in aqueous media. The kinetics of this reaction was also investigated at pH 7.0 by measuring the initial velocity V0 of the increasing concentration of O2 with a Warburg respirometer. The reaction proceeded according to the catalaselike mechanism. Fe(III)-2,9,16,23-tetracarboxyphthalocyanine supported on poly(2-vinylpyridine-CO-styrene) was a remarkably effective catalyst for a H2O2 decomposition reaction. The coordination sphere around the Fe(III)-phthalocyanine ring was characterized by electronic and ESR spectroscopy. Fe(III)-phthalocyanine supported on the copolymer dispersed in water was the five-coordinated, high-spin type. A typical competitive inhibition in respect of H2O2 by CN- was observed. ESR spectrum of this system showed the low spin iron(III) in the octahedral ligand field. The polymer coils hindered undesirable dimerization of metal-phthalocyanine molecules by the shielding effect.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220611
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  • 127
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    The photopolymerization of isoprene with the use of hydrogen peroxide as photoinitiator (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1357-1363 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photochemical polymerization reactions of isoprene with the use of H2O2 as the photoinitiator have been studied in benzene, acetone, and tetrahydrofuran solutions. Hydrogen peroxide is photodecomposed to form hydroxyl radicals which may initiate the polymerization of isoprene with hydroxyl terminated polyisoprene as the product. Average molecular weight, microstructure, and the functionality of the hydroxyl terminated polyisoprene are determined. A suitable reaction mechanism and the polymerization rate equations are proposed. The overall activations energy is evaluated to be about 3.8 kcal/mol.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220616
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  • 128
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    Polymeric arylsulfonylmethyl isocyanide, a novel polymer reagent (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1393-1407 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: p-Vinylphenylsulfonylmethyl isocyanide (1M) was synthesized starting with sodium p-styrenesulfinate via p-vinylphenylsulfonylmethylformamide (4M). Free-radical polymerization of 1M provided cross-linked insoluble polymers (1), whereas 4M provided soluble polymers, which could be converted to soluble polymer 1. Conversions of carbonyl compounds to nitriles and Schiff bases to 1,5-disubstituted imidazoles with both soluble and cross-linked polymers 1 as reagents proceeded almost as efficiently as with their low molecular weight analog. Reusability of polymer 1 was fairly good.
    Additional Material: 5 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220620
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    Effect of structure on properties of polypyromellitimide films (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1487-1494 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polypyromellitimides were prepared by the reaction of di(4-aminophenyl) ether (E)/di (4-aminophenyl) methane (M), and pyromellitic dianhydride in dimethylformamide, followed by thermal cyclization in a nitrogen atmosphere. Copolyimides were obtained by taking different molar ratios of diamines in the initial monomer feed. Differential scanning calorimetric, thermogravimetric analysis, and thermally stimulated current studies were carried out on these samples. It was concluded that the dielectric relaxation in these copolymers is due to trapping of the charge carriers. The dielectric relaxation parameters and activation energies were also calculated.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220627
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  • 130
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    Thermal properties and morphology of α-methylstyrene-butadiene-α-methylstyrene triblock copolymer (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1525-1530 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(α-methylstyrene-butadiene-α-methylstyrene) (mSBmS) was synthesized by two stages living anionic polymerization. Sodium naphthalene was used as initiator and HMPT as promoter to accelerate cross-over reactions. The microstructure and composition of mSBmS were identified by infrared and nuclear magnetic resonance spectroscopes. The domain size was roughly calculated from TEM observation. It was observed that the morphology changed with the composition. The mSBmS exhibited two Tgs, -4 and 172°C, that associated with polybutadiene and poly-α-methylstyrene, respectively. Comparing stress relaxation behaviors of mSBmS and styrene-butadienestyrene (SBS) at various temperatures, mSBmS showed a better thermal stability and degradation resistance than SBS. From the thermal gravimetric analysis, at 200°C, mSBmS gave a weight loss less than 1%, which provided a further evidence of better thermal stability of this material than of SBS.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220631
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    Preparation of silicon containing polymers. II.For Part I, see: N. D. Ghatge and J. Y. Jadhav, J. Polym. Sci. Polym. Chem. Ed., 21(11), 3055 (1983).. Effect of structure on the thermal stability of organosilicon aramidsNCL Communication No. 3323. (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1565-1572 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two silicon-containing acid dichlorides, bis(4-chlorocarbonylphenyl)dimethylsilane and bis(4-chlorocarbonylphenyl)diphenylsilane, were synthesized and reacted with 1,3-phenylene diamine, 1,4-phenylene diamine, 4,4′-diaminodiphenyl, 4,4′-diaminodiphenyl methane 4,4′-diaminodiphenyl ether, and 4,4′-diaminodiphenyl sulfone in the preparation of 12 structurally different high molecular weight aromatic polyamides. A low-temperature interfacial polycondensation technique was used. Most of the polyamides formed tough, transparent, flexible films and were characterized by solubility, solution viscosity, infrared spectroscopy (IR), and glass transition temperature (Tg). The thermal behavior of these aramids was studied by dynamic thermogravimetry. The effect of diamine and acid dichloride structure on the aramids properties is also discussed.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220704
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    Linear polythioesters. VIII.For Part VII of this series, see J. Polym. Sci. Polym. Chem. Ed., in press. Products of interfacial polycondensation of 1,4-di(mercaptomethyl)-tetramethylbenzene with isomeric phthaloyl chlorides (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1579-1586 
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    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 1,4-di(mercaptomethyl)-tetramethylbenzene with phthaloyl, isophthaloyl, and terephthaloyl chlorides were obtained. To determine the optimal conditions of 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 to organic phase, concentration of hydrogen chloride acceptor, molar ratio of reagents, rate of acid chloride addition, contribution of benzyltriethylammonium chloride as a catalyst, and the temperature of the reaction. The yield of all reaction products and the reduced viscosity of polythioesters which were soluble in the mixture of phenol-tetrachloroethane were found. A thorough examination was carried out only for the polycondensation of dithiol with isophthaloyl chloride. The structure of all polythioesters obtained under the model conditions was determined by elementary analysis and infrared spectra. Initial decomposition temperature and maximum rate of decomposition temperature were defined from the curves of thermogravimetric analysis. Some mechanical and electrical properties of the polythioesters were determined. The molecular weight was not measured because of the low solubility of the obtained polythioesters.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220706
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    Direct polycondensation of aromatic dicarboxylic acids and bisphenols with tosyl chloride and N,N-dimethylformamide in pyridine (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1653-1660 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A Vilsmeier adduct derived from arylsulfonyl chlorides and DMF in pyridine was successfully used as a new condensating agent for the synthesis of aromatic polyesters by the direct polycondensation of aromatic dicarboxylic acids and bisphenols and also of hydroxybenzoic acids. Polymers of high molecular weights (M̄w = 78,000) with relatively narrow molecular weight distribution (M̄w/M̄n ≈ 3.0) were prepared by reacting aromatic dicarboxylic acids with the adduct in pyridine, followed by addition of bisphenols. The polycondensation was significantly affected by the amount of DMF, the nature of the arylsulfonyl chlorides, the conditions of initial reaction of the acids with the adduct, and the rate of reaction with bisphenols. The process was adaptable to the direct polycondensation of hydroxybenzoic acids, affording polymers of high molecular weight (ηinh = 1.73).
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220712
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    W/O microemulsions of styrene monomer and dimer (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1699-1705 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reason for the lower water solubility in W/O microemulsions of the styrene dimer, trans, trans-1,4-diphenyl-1,3-butadiene, in comparison with the monomer was investigated by determining the phase equilibria in the microemulsion system with pentanol as the cosurfactant and sodium dodecyl sulfate as the surfactant. The main factor for the low tolerance for water in the system was the incompatibility of the dimer with the cosurfactant and surfactant.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220715
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    Flame-retardant epoxy resins based on phthalide derivative (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1707-1715 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The phthalide-containing epoxy resins are synthesized and characterized in comparison with the bisphenol-A epoxy resins in terms of thermal properties. Although both resins contain comparable amounts of halogens, the resulting flame retardancy is higher in the phthalide-containing resin. The char formation upon pyrolysis is also enhanced by the phthalide functionality.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220716
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    Solution properties of ion-containing polymers in polar solvents (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1757-1773 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The placement of ionic groups within the molecular structure of a polymer produces marked modification in physical properties. A large number of studies have been performed on these ion-containing polymers, but few have focused on the effects of anion-cation interactions (i.e., counterion binding or ionization) on hydrodynamic volume, especially as the molecular structure of the solvent and nature of counterion are varied. In this study changes in hydrodynamic volume are followed through reduced viscosity measurements as a function of the abovementioned molecular parameters.The dilute solution properties of various polyelectrolytes that contain sulfonate and carboxylate groups were investigated as a function of the counterion structure, charge density, molecular weight, and solvent structure. The polymeric materials were selected because of their specific chemical structure and physical properties. In the first instance a (2-acrylamide-2 methylpropanesulfonic acid)-acrylamide-sodium vinyl sulfonate terpolymer was synthesized and subsequently neutralized with a series of bases. Viscometric measurements on these materials indicate that the nature of the cation affects the ability of the polyelectrolyte to expand its hydrodynamic volume at low polymer levels. The magnitude of the molecular expansion is shown to be due in part to the ability of the counterion to dissociate from the backbone chain, which, in turn, is directly related to the solvent structure. The changes in solution behaviour of these inomers lend support for the existence of ion pairs (i.e., site binding) and ionized moieties on the polymer chains. Measurements performed in a variety of solvent systems further confirm this interpretation. In addition, and acrylamide-sodium vinyl sulfonate copolymer was partially hydrolyzed with sodium hydroxide to study the effect of varying the charge density at a constant degree of polymerization and counterion structure. The results show that the charge density has a significant effect on the magnitude of the reduced viscosity and dilute solution behaviour. These observations, made in aqueous and nonaqueous solvents, are related to the interrelation of hydrodynamic volume, counterion concentration, and site binding. Again the controlling factor is the degree of site binding of the counterion onto the polymer backbone. Finally, we observe that the increased hydrodynamic volume affects viscosity behavior beyond the polyelectrolyte effect regime. If the average charge density on the macromolecule is relative high and/or the molecular weight is large (≥ 106) sufficient intermolecular interactions will occur to produce rapid changes in reduced viscosity.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220720
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    A novel photoinitiator of cationic polymerization: Preparation and characterization of bis [4-(diphenylsulfonio)phenyl]sulfide-bis-hexafluorophosphate (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1789-1796 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Efforts to prepare triphenylsulfonium hexafluorophosphate by metathesis between commercially available “triphenylsulfonium chloride” and potassium hexafluorophosphate failed to yield the expected product but gave, instead, in approximately 50% yield, a crystalline substance with well-defined properties readily distinguishable from triphenylsulfonium hexafluorophosphate. The unexpected substance is identified as bis-[4(diphenylsulfonio)phenyl]sulfide-bis-hexafluorophosphate, for which no previous reference has been found in the literature. Its identification is based on elemental analysis, NMR, mass spectrometry, and infrared analysis. Bis-[4-(diphenylsulfonio)phenyl]sulfide-bis-hexafluorophosphate was also prepared by the reaction of benzene with sulfur monochloride in the presence of aluminum chloride and chlorine, followed by addition of potassium hexafluorophosphate. The product is an effective photonitiator for the crosslinking of epoxide resins.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220801
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    Substituent effects of methoxy, methyl, and vinyl groups on glow discharge polymerization (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2083-2093 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Glow discharge polymerizations in systems of trimethoxymethylsilane, trimethoxyvinylsilane, tetramethylsilane, and trimethylvinylsilane were compared by elemental analysis, infrared (IR) spectroscopy, and ESCA to reveal effects of methoxyl, methyl, and vinyl substituents. The substituent effects appeared in the chemical composition of the polymers formed especially at low W/FM values. Methoxy groups depressed the C/Si and H/Si ratios of the polymers rather than the methyl groups, whereas vinyl groups increased the C/Si and H/Si ratios. On IR spectra the polymers formed from silanes that contained methoxy groups showed fewer absorptions due to Si—H groups and strong absorptions due to Si—OH groups. The polymers from those that contained no methoxy groups showed absorptions of Si—H groups and no absorptions of Si—OH groups. These differences in the environment of Si atoms of polymeric chains also appeared in the Si2p core level spectra, thus indicating the different fragmentation patterns of the starting materials in glow discharge.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220911
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    Functional monomers and polymers. CIV.For part CIII see K. Kondo, M. Murakami, and K. Takemoto, Makromol. Chem., (1983). Synthesis and properties of oligomer models of polyethyleneimine derivatives with spacer-separated nucleic acid bases (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2061-2082 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of polyethyleneimine derivatives and their oligomer models with pendant thymine or adenine bases separated by β-alanyl groups as spacers were prepared by an activated ester method. To elucidate the nature of intramolecular interaction of thymine and adenine bases ultraviolet (UV) spectrophotometric studies were undertaken for the series of compounds and the results were compared with those obtained for the corresponding oligomers without spacers. In the thymine derivatives, the nature of the intramolecular interaction resembled that of the corresponding compounds without β-alanyl units, although larger hypochromicities were found in the series with β-alanyl units. In the adenine derivatives, contrary to the corresponding thymine systems, UV hypochromicities of the compounds decreased by incorporation of the spacer group into side chains. It became evident that the intramolecular interaction of adenine bases was due to stacking neutral species, hydrogen bonding, and residual hypochromicity for the protonated species.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220910
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    Selective separation of water-alcohol binary mixture through poly(maleimide-co-acrylonitrile) membrane (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2159-2168 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Separation of various alcohols and water through a membrane was carried out by means of a hydrogen-bonding interaction. A membrane obtained from poly(maleimide-co-acrylonitrile) was effective for a selective separation of water from aqueous alcohol solution by pervaporation technique. Spectroscopic analyses verified that this high selectivity was attributed to the hydrogen-bonding interaction between water and maleimide units in the membrane.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220917
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  • 141
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    Core-shell emulsion copolymerization of styrene and acrylonitrile on polystyrene seed particles (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2197-2215 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Seeded emulsion copolymerization of an azeotropic composition of styrene (St) and an acrylinitrile (AN) comonomer mixture in polystyrene (PS) seed at different polymerization temperature of 55-75°C were investigated. The kinetic data showed a transition temperature at 65°C, above which the activation energy of polymerization is low, 6.1 Kcal/mol, compared with 9.8 Kcal/mol below it. The particle-size results and thin layer chromatographic (TLC) data showed two types of particle of different composition and morphology in the final latex system: a smaller size of (St-AN) copolymer and a larger size of core-PS and (St-AN) copolymer shell, with a zone of PS grafted (St-AN) copolymer in between. Various polymerization parameters, that is emulsifier concentration, type of seed particle and its size, and monomer/polymer ratio, were studied and their effects on particle size and particle morphology were examined. The percent of grafted core-PS was 10% below a polymerization temperature of 65°C and 40% above that temperature. By adjusting the size and number of the seed particles, monomer-polymer ratio, and emulsifier concentration conditions were established in which a final copolymer latex with “perfect” core-shell morphology was achieved.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220921
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  • 142
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    Kinetic study of preirradiation grafting of acrylic acid onto poly(tetrafluoroethylene-perfluorovinyl ether) copolymer (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 597-604 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic study has been made on the preirradiation grafting of acrylic acid (AAc) onto poly(tetrafluoroethylene-perfluorovinyl ether) (PFA) film. The effect of grafting conditions was investigated. The dependences of the grafting rate on preirradiation dose and monomer concentration was found to be of the order of 0.5 and 1.3, respectively. The final degree of grafting was found to increase with dose and monomer concentration. However, it decreases as the grafting temperature increase. The overall activation energy for the graft polymerization was calculated from Arrhenius plots to be 5.6 kcal/mol. The activation energy for this grafting system was found to be independent of preirradiation dose used in the range from 10 to 100 kGy. The relationship between the grafting rate and film thickness gave a negative first-order dependence. The results suggest that the grafting proceeds by radical mechanism with bimolecular termination of growing chain radicals. It was reasonable concluded that this grafting proceeds from the surface to the center of film with progressive monomer diffusion through the grafted layer which swells in the monomer solution.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220309
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  • 143
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    The crosslinking of epoxy resins at interfaces. I. Germanium, germanium dioxide, and silane-treated germanium (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1495-1506 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chemical changes that accompany the crosslinking of an epoxy resin by an anhydride curing agent were followed by internal reflection spectroscopy (IRS). The crosslinking process was carried out on the surface of a germanium IRS element and the effects of various surface treatments of the germanium (humid aging, oxidation, and silane coating) on the reaction kinetics were examined. The reaction kinetics in the first 3000-4000 Å of the resin adjacent to dry, freshly polished germanium were similar to the reaction kinetics in the bulk of the resin. However, humid aging or oxidation of the germanium surface produced a local acceleration in the rate of anhydride consumption and reduced the yield of ester products. The aminosilane coating accelerated the consumption of anhydride, decreased the yield of ester, and resulted in the formation of amide groups in the interfacial region.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220628
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  • 144
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    Plasma polymerization. X. A systematic investigation of materials synthesized in inductively coupled plasmas excited in tetrafluoropyridazine (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1-16 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed investigation was made by ESCA of the gross structural features and chemical composition of ultrathin plasma polymer films prepared from tetrafluoropyridazine. The data reveal evidence of extensive rearrangement that accompanied polymerization and that the C:F and C:N stoichiometries of the polymer films were similar to those of the starting monomer. From an initially high contact angle with water the surfaces became completely wettable with time and this is attributed to surface hydrolysis. A comparison is made between surface and bulk compositions. Brief consideration is also given to sleeve effects.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220101
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  • 145
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    Radiation-induced copolymerization of phenylvinyl alkyl ethers and maleic anhydride (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 41-47 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alternating copolymers of phenylvinyl ethyl ether (I) and phenylvinyl sec-butyl ether (II) with maleic anhydride (MAn) were prepared in bulk or in benzene solution by high-energy irradiation at dose rates of 42, 160, and 540 Gy/h, respectively. The overall energies of activation in copolymerization of I and II with MAn were 15.5 and 18.8 kJ/mol, respectively. The reaction proceeds by the free-radical mechanism and was found to be largely dependent on the bulkiness of the alkyl group. In the copolymerization of I and MAn, the molecular weight increases with conversion. By applying the model described by Shirota and co-workers, it was established that participation of charge-transfer-complex monomers increases with the increase of the total monomer concentration and with the bulkiness of the alkyl group in electron donor monomer.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220104
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  • 146
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    Photoinitation of cationic polymerization. II. Laser flash photolysis of diphenyliodonium saltsFor Part I, see ref. 1. (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 69-76 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Laser flash photolysis of diphenyliodonium salts produces phenyliodinium radical cation (PhI+·), which was also generated independently by flash-induced electron transfer from iodobenzene to a phenanthrolinium salt. Apparent second-order rate constants were determined for reaction of the transient (PhI+·) with nucleophiles, including iodobenzene and cyclohexene oxide. Quantum yields of formation of acid from stationary photolysis of diphenyliodonium hexafluoroarsenate were found to be significantly higher than yields of iodobenzene. These results may be explained by facile reaction of PhI+· with PhI to yield a new iodonium salt together with a proton. High reactivity of PhI+· with cyclohexene oxide suggests that the transient may directly initiate cationic polymerization of epoxides.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220107
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  • 147
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    Solvent effects on radical homo- and copolymerizations of methacryloyl fluroride (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 85-96 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of solvent in homo- and copolymerizations of methacryloyl fluoride (MAF) was investigated in various aromatic solvents. In these solvents, there is a significant effect on the rate of polymerization, on the tacticity of the resulting poly(methacryloyl fluoride), and on the copolymerization of MAF with methyl methacrylate (MMA). The equilibrium constants between MAF and aromatic solvents were determined from NMR spectroscopic measurements. These results indicated that the solvent effect on the MAF polymerization stems from changes in reactivity of MAF induced by the strong MAF-solvent interaction as well as stabilization of the MAF radical by solvents. Copolymerization of MAF with both p-methoxystyrene (MSt) and p-nitrostyrene (NSt) was also studied.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220109
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    Synthesis and attempted polymerization of N-arylmaleimides substituted with allylamino or cyclopropylamino groups at 2-positionThis article is taken in part from the Masters thesis of H. Kaleefa, Department of Chemistry, College of Science, University of Baghdad, Baghdad, Iraq, 1983. (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 129-134 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several N-substituted chloromaleimides were prepared by dehydrating the corresponding chloromaleamic acids. Treatment of chloromaleimides with allylamine or cyclopropylamine produced N-aryl-2-(allylamino)maleimides and N-aryl-2-(cyclopropylamino)maleimides, respectively. Neither the N-substituted chloromaleimides nor the N-aryl-2-(allylamino) or N-aryl-2-(cyclopropylamino)maleimides polymerized free radically or anionically. The difficulty of achieving good pi-pi overlap and stiric effects at the propagation step prevented the cyclopolymerization of the prepared 1,5-dienes.
    Additional Material: 5 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220113
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  • 149
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    Organosilane polymers: Formable copolymers containing dimethylsilylene units (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 159-170 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Formable silane copolymers that contain dimethylsilylene units were synthesized and characterized. These polymers have high molecular weights and appreciable solubility in common solvents, can be molded or cast into films or drawn into fibers, and are photoactive.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220116
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  • 150
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    Radiolysis of resist polymers. III. Copolymers of methyl-α-chloroacrylate and trihaloethylmethacrylates (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 195-211 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Homopolymers of 2,2,2-trifluoroethyl(methacrylate) (TFEMA) and 2,2,2-trichloroethyl-(methacrylate) (TCEMA) and copolymers with methyl-α-chloroacrylate (MCA) in a range of compositions were synthesized. The reactivity ratios were obtained; the two copolymerizations were close to ideal. Poly(MCA) showed Gs = 7.4 and Gs = 0.9 by γ-radiolysis. On the other hand, poly(TFEMA) and poly(TCEMA) and Gs values of 2.0 and 2.4, respectively, and Gx = 0. Radiolysis of copolymers was initiated to a large degree by dissociative electron capture by the halogen atoms in both comonomers, as revealed by the ESR spectra of radicals derived from them. Germinal recombinations in irradiated poly(TFEMA) suggested the presence of radicals in proximity. This process was absent in the copolymers. GC-MS analysis of volatile products and other supporting evidence showed that TFEMA monomers tended to depolymerize; the TCEMA monomers did not. The radiolysis yields varied monotonically with the comonomer composition for the MCA-TFEMA system but the yield-composition relationship was irregular in MCA-TCEMA copolymers. Four noncrosslinking systems are potential radiation resists arranged in increasing order of promise: poly(TFEMA) (Gs = 2.0, Tg = 70°); poly(TCEMA) (Gs = 2.7, Tg = 142°); poly(94MCA-co-6TCEMA) (Gs = 2.7, Tg = 142°); and poly(68MCA-co-32TFEMA) (Gs = 3.0, Tg = 112°). These materials merit further investigation for E-beam or x-ray lithographic applications. Mechanisms of radiolysis for these materials, based on ESR, GC-MS, and radiolysis yield data, were discussed.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220119
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  • 151
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    Lyotropic mesophases of hydroxypropylcellulose in pure acetic acid, in water, and in mixed solvents (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 239-247 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photomicrographys of concentrated lyotropic hydroxypropylcellulose solutions confirm the cholesteric nature of the anisotropic phases in acetic acid and water. They reveal the existence of biphasic separation. Typical liquid-crystal solvent-dependent textures are observed. The behavior of liquid-crystalline phases in mixed solvents is also studied, and the cholesteric pitch of the twist structure is measured for various relative concentrations of solvents. Spherical droplets, or “spherulites,” in well-defined relative concentrations of solvents have been observed.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220122
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  • 152
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    On the reaction of linear and crosslinked polystyrene with 1,4-bis(chloromethoxy)butane (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 269-275 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chlorometylation of linear and crosslinked polystyrene with 1,4-bis(chloromethoxy) butane was studied, and the behavior of 1,4-bis(chloromethoxy)butane in the presence of chloromethylation catalysts was also established by 1H-NMR spectroscopy.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220125
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  • 153
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    Polyaromatic ether-ketone sulfonamides prepared from polydiphenyl ether-ketones by chlorosulfonation and treatment with secondary amines (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 295-301 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyaromatic ether-ketone sulfonamides with potentially open structures of interest for membranes were prepared from polyaromatic ether-ketones by sulfonation with chlorosulfonic acid, followed by amination with various amines. Various degrees of substitution were achieved by controlling the reaction conditions of sulfonation. These polymers are soluble in solvents like dimethylformamide, dimethylacetamide, and chloroform and can be cast into transparent films.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220202
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  • 154
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    Copolymerization of ethylene with higher linear α-olefins - reactivity ratios (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 333-340 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolymerization of ethylene with mixtures of linear α-olefins C6-C36 in the presence of two heterogeneous Ziegler-Natta catalysts, δ-TiCl3-AlEt3 and TiCl4/MgCl2-AlEt3, at 90°C was studied by the GC method, and reactivity ratios for all paris ethylene-α-olefin were estimated from the data on olefin consumption in the reactions. In the case of the δ-TiCl3-AlEt3 system, the r2 value decreases from ca. 0.05 for 1-decene to ca. 0.02 for α-C22H44 and then remains approximately constant. This change is similar to the dependence of the modified steric parameter ESC of the olefin alkyl group on the size of the alkyl group. In the case of the supported TiCl4/MgCl2-AlEt3 system a similar variation of r2 with the length of the alkyl group were observed but the absolute values of r2 were six to ten times lower than those for the first catalytic system.
    Additional Material: 6 Ill.
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  • 155
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    Functional monomers and polymers. CXVII.For Part CXVI, see J. H. Liu, K. Kondo, and K. Takemoto, Angew. Makromol. Chem., 121, 109 (1984). Photochemical reactions on oligo- and polyethyleneimines containing pendant thymine bases: Effect of the spacer (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2427-2442 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photodimerization reaction of thymine bases incorporated in the modified oligo- and polyethyleneimines, in which α-alanine or ß-alanine unit was inserted between the main chain and the pendant thymine bases, was studied both in aqueous and in dimethyl sulfoxide solutions. It was found that the quantum yields for the photodimerization for the oligomers were closely related to the intramolecular interaction in the ground state, while those of the copolymers were not related to the ground state interaction. It was suggested that the singlet energy migration was present in the case of the polyethyleneimine derivatives. This result is discussed in terms of the effects of the nearest-neighboring thymine units, the structure of the side chain, and the singlet energy migration, particularly for the copolymers.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170221012
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    Complexation and rate of polymerization of acrylic acid and methacrylic acid in the presence of poly(4-vinylpyridine) in dilute methanol solution (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2479-2487 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A 1:1 hydrogen-bonded complex was formed between acrylic acid (AA) or methacrylic acid (MA) and the pyridine group of poly(4-vinylpyridine) (P4VP) in dilute solutions. A shift of infrared absorption of the hydrogen-bonded acid O—H to a lower energy direction and an upfield shift of acid proton in the NMR were observed when the monomers were added with pyridine. The equilibrium constants of the 1:1 complexation with P4VP measured by using a semipermeable membrane were 0.58 and 0.26 for AA and MA, respectively, at 25°C in methanol. The bromometrically measured initial rate of radical polymerization showed only a slight enhancement in the presence of P4VP, the rate being maximum at the 4VP unit:monomer mole ratio of 0.25 and 0.5 for AA and MA, respectively, in dilute methanol solution at 60°C.
    Additional Material: 7 Ill.
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    Optical rotatory dispersion and circular dichroism studies of copoly(propyl-L-aspartate-benzyl-L-aspartate) (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2533-2538 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copoly(propyl-L-aspartate-benzyl-L-aspartate)s with various compositions were synthesized by propylation of a parent poly(β-benzyl-L-Aspartate). The variation of helix sense of copolyaspartate obtained against a degree of propylation and temperature was examined by optical rotatory dispersion and circular dichroism method. Copolyaspartate of propylation less than about 70% is in a left-handed α helix conformation and its Moffitt parameter b0 and molecular ellipticity [θ]222 decreased gradually with increasing propylation. On the other hand, a different temperature dependence of b0 and [θ]222 was observed for copolyaspartate of propylation more than about 80%, i.e., the reversible transition of the helix sense from right- to left-handed α helix took place by temperature increasing. These features were basically similar to the variation in helix sense of copoly(ethyl-L-aspartate-benzyl-L-aspartate), although a slight difference was seen for copoly(propyl-L-aspartate-benzyl-L-aspartate). The thermodynamic treatment indicating larger entropy of right-handed α helix suggests much mobile side chain of the right-handed α helix than the left handed one.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170221020
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    Reactions in the presence of organic phosphites, I: High temperature amidation in the absence of solvents (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2567-2577 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When reacted for periods of 5-10 min at temperatures of about 280-300°C in the presence of certain organic phosphites polymers that contain available carboxy and aliphatic amine groups undergo amidation. This reaction can increase the molecular weight of many aliphatic polyamides by their self-reaction in an extruder. Block or graft copolymers can be formed by reacting polymers that contain aliphatic amines with others that contain carboxyl. Studies of model compounds in the companion article (II) indicate that polymerization proceeds through an diaryloxy or dialkoxy amino phosphine intermediate to produce amide bonds and disubstituted phosphite reaction by-products. In the absence of primary amines in the reaction mixture an ester is slowly formed from the carboxyl end group of the polymer and the oxysubstituent of the phosphite. In no case was a phosphorus-containing mixed anhydride detected. The mechanistic identity of the low temperature reactions in article II and the high temperature reactions in this article has not been proved conclusively, however.
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  • 159
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    Catalyseurs Zieger-Natta supportés sur MgCl2 pour la polymérisation stéréorégulée du propène. II. Système catalytique simple: Solide binaire MgCl2-TiCl4 et solution cocatalytique triéthylaluminium, benzoate d'ethyle (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2625-2640 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of propene polymerization in heptane slurry at 1-4 bars was studied with a catalytic system that consisted of a solid catalyst prepared by adsorption of TiCI4 on pure porous MgCl2 (by dehydrating MgCl2, 6 H2O with thionyl chloride) and a cocatalytic, heptanic solution of ethylbenzoate (BE) and triethylaluminium (TEA). At a temperature approaching 60°C/polymerization began immediately after the introduction of the monomer. The polymerization rate decreased continuously during the reaction. The loss in activity, however, was not due to a diffusional effect (e.g., blocking of the catalyst by the growing polymer). Studies of the ageing of the catalytic system showed a deactivation of the catalytic system itself as a function of the time of contact between the catalyst and the cocatalyst. The product of the thermal decomposition of the complex 1:2 formed by the reaction of BE with TEA was not associated with the deactivation process or stereospecific control, which depend on the BE/AI ratio and the presence of the complex.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170221028
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    Mechanisms of polymer-supported catalysis. 5. Solvation of quaternary onium ions in polystyrene gels by 13C-NMR spectroscopy (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 509-518 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C-NMR linewidths and spin-lattice relaxation times have been determined for soluble and crosslinked polystyrenes containing quaternary phosphonium and ammonium ions. Solubilities and NMR linewidths show that the solvating abilities toward tri-n-butylphosphonium ions are CDCl3 〉 CH3OH 〉 D2O 〉 benzene, toluene, toward the trimethylammonium ions, CH3OH 〉 CDCl3 〉 D2O 〉 toluene, and toward the nonpolar polymer backbone, CDCl3, benzene 〉 toluene 〉 CH3OH 〉 D2O.
    Additional Material: 5 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220301
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    Hydrophilic polymer-immobilized lipoamide-iron (II) system as a new reducing catalyst for the reduction of O-benzylhydroxylamine by sodium borohydride (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2733-2733 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221039
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  • 162
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    Applicability of the Mayo-Lewis equation to high conversion copolymerization of styrene and methylmethacrylate (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2777-2788 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In contradiction to reports from this and other laboratories, this study reports that the integrated Mayo-Lewis equation, or Meyer-Lowery equation, adequately describes the high-conversion free radical copolymerization of styrene and methylmethacrylate. The copolymerization was monitored by following the changes in the feed composition using NMR, as well as determination of the resulting copolymer compositions by NMR and UV. “Error in all Variables” statistical techniques were used to produce estimates of the reactivity ratios. The reactivity ratios estimated were, from feed composition, NMR, r1 (styrene) = 0.472, r2 = 0.454, from copolymer composition, UV, r1 = 0.497, r2 = 0.464, and NMR, r1 = 0.432, r2 = 0.422.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221104
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  • 163
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    A convenient photochemical method to immobilize enzymes (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2817-2828 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method to immobilize enzymes photochemically with use of photocrosslinkable poly(vinylalcohol) bearing stilbazolium groups is described. Irradiation of a film of the photosensitive polymer containing enzyme gave water-insoluble, cellophane-like transparent film demonstrating high enzyme activity. The dissolution of enzymes from the film was dependent upon the molecular weight of the proteins and the content of the photocrosslinking unit. It was found that various enzymes are sufficiently entrapped in the photocrosslinked polymer matrix when the content of the photosensitive group is more than about 1.0 mol%.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221108
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  • 164
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    The use of organotin compounds in the thermal stabilization of poly(vinyl chloride). VI. An assessment of the relative importance of HCl-scavenging, exchange, and addition reactions (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2871-2886 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of PVC with three representative stabilizers Bu2SnY2 (Y = OCOC11H23, SCH2COOCH2CH(Et)CH2CH2CH2CH3, OCOCH=CHCOOMe) in solution and under nitrogen were studied by two principal methods. First, using stabilizers with radioactive labels in the Y groups, the uptake of these groups by virgin and degraded polymer was measured. The UV-visible absorption spectra of the stabilized polymers are discussed. Second, the effect of these three stabilizers on the rate of elimination of hydrogen chloride from heated PVC was studied. It is shown that the effects of HCI-scavenging and of exchange reactions in suppressing the evolution of HCI can be separately evaluated. The thermal decomposition of dibutyltin bis(methyl maleate) to give maleic anhydride is reported. Interpretation of the observations is made in terms of assessing the relative importance of the various polymer-stabilizer reactions in promoting stabilization.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221112
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  • 165
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    Preparation and characterization of plasma-polymerized styrene thin films (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2953-2972 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Plasma-polymerized styrene (PPS) thin films (several hundred to several thousand Å thick) have been prepared under a variety of discharge conditions in a tubular reactor inductively coupled to a radio frequency (13.56 MHz) power supply. Studies have focussed on the correlation of deposited polymer structure, evidenced both at the film surface (via XPS analysis) and in the bulk polymer (via transmission FT-IR analysis) with controllable plasma parameters (coupled rf power, monomer flow rate, monomer pressure). It has been determined that the relative number of phenyl rings incorporated into the film intact is an inverse function of the power per styrene molecule ratio. Polymer deposition rate was found to be a strong function of styrene flow rate and substrate temperature. Plausible elements of the styrene plasma polymerization mechanism will be considered.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221119
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  • 166
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    Dual functional catalysis for ethylene polymerization to branched polyethylene. I. Evaluation of catalytic systems (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3027-3042 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of low-density polyethylene, that is, a density of less than 0.925 g/cm3, has traditionally been accomplished by the use of free-radical initiators at high ethylene pressures or of an alpha olefin comonomer such as 1-butene at lower pressures. We investigated an alternative route to branched, low-density polyethylene with a single monomer, ethylene, as the feed in conjunction with multicomponent catalyst systems capable of in situ dimerization of ethylene and subsequent copolymerization to produce low-density polyethylene. This article discusses the details of the evaluation of a number of dual-functional systems based on Ziegler-Natta catalysts. Specific, well defined, dual-functional catalyst systems which could easily produce branched, low-density polyethylene with levels of 20-30 branches per 1000 carbon atoms were developed. Variations in the relative number of component catalysts resulted in systematic, predictable changes in the properties of the polyethylene produced, which demonstrated the utility of the dual-functional catalyst concept.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221125
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  • 167
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    Acyloin condensation of terephthaloyl chloride - a novel route to polyhydroxyketones (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3107-3113 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acyloin condensation of terephthaloyl chloride under homogeneous conditions using a sodium naphthalene radical anion system and under heterogeneous conditions using finely dispersed molten sodium with varying ratios of sodium to organic substrate gave mainly polymeric materials that were identified as polyhydroxyketones. IR, NMR, and DTA analyses indicate that these polymers are copolymers of benzoin and benzil hitherto unknown. The yields of polymers under homogeneous conditions were higher than those obtained under heterogeneous conditions, but the molecular weight distribution was similar to those obtained with molten sodium.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221130
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  • 168
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    Anionic polymerization of lactones initiated by alkali graphitides. III. Polymerization of δ-valerolactone initiated by KC24 (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 905-910 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The anionic polymerization of δ-valerolactone initiated by KC24 in xylene or tetrahydrofuran was investigated. The influence of the polymerization conditions on the amount and composition of the oligomers fraction and high polymers formed was tested. Experiments were done with a potassium mirror and benzophenone-potassium as initiators of the polymerization to check the influence of the layered structure of the initiator. It was found that the amount of the oligomers formed under comparable conditions increases in the order KC24 (9%), potassium mirror (22%), benzophenone-potassium (56%). The highest yields of poly(δ-valerolactone) (over 90%) and highest intrinsic viscosities (1.0 dL/g and more) were achieved by the KC24-initiated polymerizations in xylene.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220402
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  • 169
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    Solid products from thermal decomposition of polyethylene terephthalate: Investigation by CP/MAS 13C-NMR and fourier transform-IR spectroscopy (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 945-957 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solid reaction products from pyrolysis of polyethylene terephthalate in the presence and absence of red phosphorus were characterized by CP/MAS 13C-NMR, FR-IR, and MAS 31P-NMR spectroscopy. Over the temperature range of 300-400°C, polyethylene terephthalate was converted in a sealed vial to a highly crosslinked polymer of terephthalic acid. Pyrolysis in the presence of red phosphorus, which functions as a flame retardant by increasing the amount of char, yielded an intractible polyaromatic phosphate ester. After thermal cleavage of polyethylene terephthalate with formation of free carboxyl and vinyl ester groups, there are two competing reaction pathways. The smaller molecular weight fragments may enter the vapor phase where they undergo further degradation primarily to CO2, CO, and acetaldehyde, as described by others. However, if volatilization of the oligomeric fragments is inhibited, an alternate reaction pathway gives rise to the formation of highly crosslinked char. Red phosphorus decreases the volatility of the oligomeric fragments by converting them to phosphates and thereby enhances char formation.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220405
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  • 170
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    Polymerization of terminal alkynes by a new Ziegler-Natta catalyst system: Scandium naphthenate/trialkylaluminum (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1009-1015 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The scandium naphthenate/trialkylaluminum system was investigated as a catalyst in the polymerization of substituted alkynes. Phenylacetylene was converted to a moderately crystalline, high cis polymer. The alkyl-substituted acetylenes produced rubbery or solid materials of relatively high molecular weight. Infrared (IR), ultraviolet (UV), 1H-NMR, and 13C-NMR studies of the polyalkylacetylenes revealed high cis conformation, but apparently twisted from planarity to decrease molecular orbital overlap in the polyconjugated chain.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220501
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  • 171
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    Preparation and some properties of nylon-4,2 (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1373-1382 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An attempt was made to produce a new short-chain alphatic polyamide nylon-4,2. This polyoxamide can be prepared by polycondensation of tetramethylene diamine and diethyl oxalate. A high molecular weight polymer (ηinh = 1.9 from 0.5% solutions in 96% sulphuric acid) has been obtained by employing a two-step polycondensation method; the precondensation was carried out in solution at low temperatures (20-140°C) and the postcondensation in the solid state at high temperatures (250-300°C). The effect of solvent composition and reaction temperature on the prepolymerization and the effect of reaction time and temperature on the postcondensation was studied. We also investigated the influence of moisture during washing, storing, and the solid-state reaction on the polymerizability by the postcondensation. Nylon-4,2 is soluble only in highly polar solvents such as trifluoroacetic acid (TFA), dichloroacetic acid, and 96% sulphuric acid. Films were cast from TFA. With these films we studied the IR spectrum, WAXS pattern, water absorption, and melting behavior. Nylon-4,2 was found to melt at 388-392°C, has a crystallinity of 70%, and a low water absorption (3.1% at 50% RH). The glass transition temperature of the dry sample was found to be at ∼120°C and for the wet sample at -15°C.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220618
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  • 172
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    Addition polyimides. III. Thermal behavior of bismaleimides (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1419-1433 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This article describes the synthesis of N,N′-bis(3,3′-maleimidophenyl) sulfone (S) and its Michael addition products with (4,4′-diaminodiphenyl) methane (S-M), 4,4′-diaminodiphenyl ether (S-E), (3,3′-diaminodiphenyl) sulfone (S-DDSm), (4,4′-diaminodiphenyl) sulfone (S-DDSp), (3,3′,3″-tris aminophenyl) phosphine oxide (S-TAP), and 9,9-bis(p-aminophenyl) fluorene (S-B). Curing behavior of these bisimides was investigated by differential scanning calorimetry. Activation energy of curing reaction was determined by using isothermal and multiple heating rate method. Thermal stability of bisimides was evaluated by thermogravimetric analysis. Better char yields were obtained in S-TAP resins.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220622
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  • 173
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    Molecular weight phenomena at high conversions in the Ziegler-Natta polymerization of butadiene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1461-1470 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A Comparison between two different feedstocks in the homogeneous polymerization of butadiene has been conducted. The conversion and molecular weight trends were essentially the same for both feedstock systems. Changes in polydispersity at high conversions could not be explained by a living polymerization mechanism. A reaction scheme involving reuse of active cobalt centres combined with termination has been proposed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220624
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  • 174
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    DTA studies on the thermal oxidation and crosslinking reactions of carboxyl-terminated polybutadiene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1481-1486 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies on the thermal oxidation of carboxyl-terminated polybutadiene in the presence of antioxidants have been carried out by dynamic DTA. Bis-thioacetylacetonato nickel(II) compounds are found to be effective in inhibiting the air oxidation reaction in the polymer. The crosslinking reaction of the polymer through the double bonds present in the polymer molecule is desensitized by the antioxidants and the effect is more with N-phenyl-1-naphthylamine. An exothermic peak formed at 270°C in the presence of tris(2-methylaziridinyl-1) phosphine oxide has been identified as the curing reaction. The infrared spectra of CTPB in the presence of MAPO at various temperatures confirm the various stages of reaction.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220626
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  • 175
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    Poly(m-phenylene isophthalamides)-containing nitro groups (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1531-1533 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220632
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  • 176
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    Structure and electric conductivity of vapor deposition polymerization products of cyanoacetylene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1551-1564 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyanoacetylene can be polymerized from the vapor state onto an inactive surface of substrate at a temperature as low as 200°C. The polymerization first occurs by way of the carbon-carbon triple bond. The reaction product obtained at 1000°C contains nitrogen at a concentration as high as 13.7%. At least some of this nitrogen is in naphtiridine ring or rings similar to it. The product obtained at 400°C is amorphous, while the product obtained at 1000°C has at least partly graphite-like crystalline structures with an apparent crystallite size (Lc) of about 17 Å. The electric conductivities of the products obtained at 400, 700, and 1000°C are 7.7 × 10-2, 91, and 1600 S/cm, respectively. These values are extremely high compared to the pyrolized PAN treated at the same temperature. Electric conductivity of the product obtained at 400°C is well explained by the variable range hopping model in 3-dimensional amorphous materials. With the products obtained at the higher temperatures, conductivity cannot be accounted for by the hopping model. This is probably due to the development of graphite-like structure.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220703
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  • 177
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    Syntheses of poly[N-(1-pyrenyl)acetyl ethylenimine] [pyrene-substituted linear poly(ethylenimine)] and poly[methyl 2-(1-pyrenyl)acetamidopropenoate] [pyrene-substituted poly(dehydroalanine methyl ester)] (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1587-1602 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The syntheses of two new pyrene-containing monomers - 2-(1-pyrenyl)methyl-2-oxazoline (6) and methyl 2-(1-pyrenyl)acetamidopropenoate (12) - and their polymerization are described. Cationic isomerization polymerization of 6 with ethylene glycol ditosylate initiator gave poly[N-(1-pyrenyl)acetyl ethylenimine] (7) and free-radical polymerization of 12 with AIBN initiator gave poly[methyl 2-(1-pyrenyl)acetamidopropenoate] (15). The monomer model compounds of the two polymers, namely, N,N-diethyl(1-pyrenyl)acetamide (9) and methyl 2-methyl-2-(1-pyrenyl)acetamidopropanoate (14), were also synthesized. The polymers were characterized by elemental analysis, IR spectroscopy, and a comparison of their 1H-NMR spectra with those of the respective monomer model compounds.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220707
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  • 178
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    Kinetics of polymerization of methyl methacrylate initiated with cyclohexanone. Part I (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1891-1895 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of radical polymerization of methyl methacrylate were investigated in a dioxane solution with cyclohexanone as initiator. It was found that the overall rate of reaction initiated with cyclohexanone (Rp) is proportional to the concentration of monomer and to the square root of the concentration of the initiator. The effect of temperature on the Rp in the temperature range of 65-95°C was discussed. The Arrhenius activation energy Ea estimated for the temperature range of 65-75°C was 137 kJ mol-1.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220811
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  • 179
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    Polymerization initiated by ylide: Polymerization of ethyl methacrylate with the use of 4-picolinium p-chloro phenacylide as initiator (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1875-1882 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ylide 4-picolinium, p-chloro phenacylide-initiated thermal polymerization of ethyl methacrylate (EMA) was studied. 4-Picolinium p-chloro phenacylide induces the thermal polymerization of ethyl methacrylate at 65°C. The rate of polymerization (Rp) rose as the initiator concentration increased from 2 × 10-3 to 4 × 10-3 M and the initiating exponent was computed as 1.9. The Rp decreased as the concentration of ylide increased from 6 × 10-2 to 1M. The greater initiator concentration also affected the molecular weight inversely. The polymerization was carried out at different temperatures and the overall activation energy was computed as 4.08 Kcal/mol. Polymerization was inhibited in the presence of hydroquinone as a radical scavenger. Kinetic studies and other data show that the overall polymerization takes place in a radical mechanism. The various kinetic parameters, such as the rate and average degree of polymerization, molecular weight, and energy of activation of the present system, were evaluated.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220809
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  • 180
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    Preparation and properties of N-phenylated aromatic polyamide-esters from anilinophenols and aromatic diacid chlorides (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1981-1986 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-Phenylated aromatic polyamide-esters with high molecular weights were synthesized by the high-temperature solution polycondensation in nitrobenzene at 200°C from combinations of m- and p-anilinophenol and isophthaloyl and terephthaloyl chloride. Reaction variables such as monomer concentration, solvent, temperature, and time were studied to optimize the reaction conditions for the preparation of high molecular weight polymers. Some of the N-phenylated aromatic polyamide-esters have glass transition temperatures around 190°C and good solubility in chlorinated and amide solvents. These polymers gave transparent flexible films by solution-casting. Copolymers from p-anilinophenol and the two diacid chlorides were also synthesized and characterized.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220903
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  • 181
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    Copolymers of vinylamine and vinylalcohol by acid hydrolysis of poly(N-vinyl-tert-butylcarbamate-co-vinylacetate): Evaluation of reactivity ratios (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2353-2362 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolymers of vinylamine and vinylalcohol were prepared by hydrolysis of poly(N-vinyltert-butylcarbamate-co-vinylacetate) in 1:1 v/v % ethanol/HCl mixtures at room temperature. Reactivity ratios of the monomers N-vinyl-tert-butylcarbamate (1) and vinylacetate (2) were calculated from monomer feed and copolymer composition data, according to the methods of Fineman-Ross and Kelen-Tüdös, yielding r1 = 1.14 ± 0.05, r2 = 0.47 ± 0.07, and r1 = 1.12 ± 0.07, r2 = 0.46 ± 0.03, respectively. From these values the average sequence length distribution of monomer units was derived showing that in the raction of N-vinyl-tert-butyl carbamate and vinylacetate nearly Bernouillian (i.e., purely random) copolymers are formed, with a slight tendency toward alternation.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221006
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  • 182
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    Synthesis and polymerization of optically active L-[α-(N-p-acryloxybenzoyl)alanine ethyl esters] (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2413-2425 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New optically active monomers L-[α-(N-p-acryloxybenzoyl)alanine ethyl esters] (I) and their polymers were synthesized. The title monomers (I) were prepared by the reaction of 1-p-acryloxybenzoyloxy-4-chlorobenzotriazoles (II) with L-alanine ethyl ester hydrochloride, by aminolysis of the active monoester. The new typical active ester (II) was synthesized by the N-hydroxy compound active-ester methods in excellent yield. Before the synthesis of the optically active monomers was carried out, a model study of the aminolysis of the two active esters was performed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221011
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  • 183
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    Poly(sodium styrene sulfonate-alt-sodium-N(4-sulfophenyl)maleimide): A new water-soluble alternating copolymer (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2281-2285 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220928
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  • 184
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    Studies on vinyl photopolymerization using a macromolecular C.T. Complex between poly(N-vinyl carbazole) and bromine as the photoinitiator (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2295-2303 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photopolymerization of methyl methacrylate (MMA) was studied at 40°C using a macromolecular C.T. Complex between poly(N-vinyl carbazole) and bromine, expressed in brief as (PNVC-Br2) complex, as the photoinitiator. Initiator exponent was 0.40 for [PNVC-Br2] ≤ 2.5 × 10-3 mol L-1 and practically zero for [PNVC-Br2] 〉 2.5 × 10-3 mol L-1. Monomer exponent in different diluent systems such as benzene, carbon tetrachloride, and acetone was close to 1.0. Low initiator exponent (〈0.5) is explained on the basis of an initiator-dependent termination mechanism, in addition to the usual bimolecular termination. Analysis of kinetic data indicates that the initiator-dependent termination is primarily due to degradative initiator transfer and that due to primary radicals is considered inconsequential in view of monomer exponent being close to unity. The non-ideal termination process assumes over-whelming prominence at high [PNVC-Br2].
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221001
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  • 185
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    Crown ethers as ligands for stereospecific polymerization by Ziegler-Natta catalysts (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2345-2352 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Some new TiCl4/Crown ether complexes were synthesized and used as polymerization catalysts with AlEt3 or AlEt2Cl as cocatalyst for the stereospecific polymerization of 1,3-butadiene. As with most of the nucleophilic ligands the addition of crown ethers to Ziegler-Natta catalytic systems results in a decrease of the polymer conversion. But the Al/Ti molar ratio appears to be less critical for the complexed systems than for the uncomplexed ones. The presence of the crown ether in the surroundings of the catalytic sites presumably protects them from an excess of the organoaluminum cocatalyst. The side groups of the crown ether do not influence the microstructure of the polybutadiene obtained but they change the activity of the catalytic systems. Thus, the electron-donating effect of the macrocyclic ligands seems to be less important than the sterical effect due to the rigidity and to the hole size of the crown ether.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221005
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  • 186
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    Ablative photodecomposition of polymer films by pulsed far-ultraviolet (193 nm) laser radiation: Dependence of etch depth on experimental conditions (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2601-2609 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Data on the ablative photodecomposition of three condensation polymers [polyimide, poly(ethylene terephthalate), and polycarbonate] and one addition polymer (polymethyl methacrylate) by laser pulses at 193 nm are presented. The etch depth/pulse is a linear function of the number of pulses at constant laser fluence. It varies with the logarithm of the fluence in a linear manner at different fluences. The etch depth is independent of the atmosphere above the film, whether it is air at 1 atm, or a vacuum. The etching of PMMA at fluences 〉 100 mJ/cm2 is believed to follow a mechanism different from the process at lower fluences. Etching of polyimide and polyethylene terephthalate at 248 and 308 nm is also reported. The mechanism of etching by laser radiation may receive greater contribution from a thermal process with increasing wavelength. This is manifested in the etch depth versus log fluence plot by sharp changes in slope.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221026
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  • 187
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    Three-component interpenetrating polymer networks (IPN's) from polyurethanes, epoxies, and poly(methacrylates) (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2667-2683 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three-component IPN systems made from polyurethanes, epoxies, and poly(methacrylates) containing charge groups in the backbones of the constituent networks have been prepared. Specific attractive forces that occurred among the various networks helped to compatibilize them and aided in the formation of true homogeneous topologically interpenetrating polymer networks. These three-component polymer alloys, including full-IPN's, pseudo-IPN's, and graft-IPN's, were characterized by means of mechanical spectroscopy, electron microscopy, and stress-strain properties. In addition, some adhesion studies were carried out (lap shear strength and peel strength). A comparison of the different types of three-component polymer alloys showed that better properties were generally exhibited by the graft-IPN's and full-IPN's containing opposite charge groups.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221031
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  • 188
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    Synthesis of aromatic polyesters by direct polycondensation with triphenylphosphine dichloride (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2705-2712 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aromatic polyesters of high molecular weights were prepared by the direct polycondensation reaction of dicarboxylic acids and bisphenols or hydroxybenzoic acids with triphenylphosphine dichloride as a new condensing agent. Reaction conditions, including the amount of reagents and the concentration of monomer, solvent, and acid acceptor, were investigated. The aromatic polyester with the solution viscosity of 1.66 dL/g was obtained from bisphenol. A and terephthalic and isophthalic acid in quantitative yield under the optimum condition. The principal advantage of this condensing agent is that, based on the recycling system, recovered triphenylphosphine oxide can be reconverted to the reactive triphenylphosphine dichloride by treating with phosgene or oxalyl chloride.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221034
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  • 189
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    Polymerization of methyl methacrylate initiated by a ceric ion-isopropyl alcohol redox system (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2729-2732 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221038
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  • 190
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    Compatibility in poly(ethylene oxide)-poly(methyl methacrylate) blends (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2809-2815 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The compatibility of poly(ethylene oxide)-poly(methyl methacrylate) (PEO-PMMA) blends were examined covering the complete composition range. Up to 20% of PEO content films were transparent and glass transition temperatures were determined by DSC and by refractive index vs. temperature measurements. Only one Tg was obtained for these samples and the relationship between Tg and composition has been evaluated. At higher PEO content crystallization took place and the films were opaque. Melting temperatuures of PEO in blends were determined by DSC. Melting point depression was observed for increasing proportion of PMMA and the binary interaction parameter has been calculated.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221107
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  • 191
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    Superacid polymers from sulfonated poly(styrene-divinylbenzene): Preparation and characterization (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2859-2870 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Superacid polymers were prepared by bringing metal halides (AlCl3, SnCl4, TiCl4, BF3, or SbF5) in contact with macroporous sulfonic acid resins [sulfonated, crosslinked poly(styrene-divinylbenzene)]. The resulting solids were characterized by chemical analysis, temperature-programmed desorption, transmission electron microscopy, and X-ray photoelectron spectroscopy. They were also tested as catalysts for n-butane isomerization at 0.5 bar and 60 to 120°C. The polymers consist of supported metal oxyhalide particles, complexes of metal oxyhalides and sulfonate groups, and the remaining unreacted sulfonic acid groups. In the presence of HCl, these polymers were highly active catalysts for the butane isomerization reaction, the activity being a consequence of a high proton-donor strength inferred to be associated with H2Cl+ groups stabilized on the polymer surface by negative charge delocalization over sulfonate-metal oxyhalide sulfonate groups.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221111
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  • 192
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    Solid-state polymerization of butadienes. Crystal structure and solution properties of a stereoregular amphoteric 1,4-trans-polybutadiene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2895-2921 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The double salt 1 consisting of the hydrochloride of 6-amino-2,4-trans-hexadienoic acid and cadmium chloride in a 2:1 stoichiometry polymerizes in the crystalline state if exposed to UV or γ irradiation. A stereoregular polymeric ampholyte is formed in an extended chain macroconformation, embedded in an inorganic matrix. The crystal structure of the polymerized crystals and the solution properties of the polymer are reported. Polymerized crystals are triclinic, space group P1, a = 7.2144 Å, b = 7.2447 Å, c = 18.5936 Å, α = 104.49°, β = 96.631°, γ = 95.706°, Z = 2. The structure consists of 2-dimensional layers of polymer and inorganic CdCl6 octahedra alternatively stacked in the third dimension. The cadmium ions can be separated from the polymer by a precipitation as insoluble CdS. After separation from the inorganic material the polymer is soluble in strong acids and bases and insoluble in neutral water. From viscosity measurements of alkaline solutions of the polymer, an average molar mass of 4 × 104 g/mol can be deduced. The polymer selectively adsorbs divalent transition metal ions if suspended in an aqueous solution of transition metal salts. The structure of the resulting polymer-metal complexes is discussed.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221114
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  • 193
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    PVC miniemulsion polymerization II. Particle and droplet growth as a function of conversion (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2931-2939 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Growth of two droplet families and a polymer seed family as a function of percent monomer conversion in PVC miniemulsion synthesis demonstrates that polymerization in droplets predominates to ∼ 30-40% conversion, whereupon polymerization of seed becomes favored. This difference appears to be due to a liquid-to-solid phase change in the forming particles during the course of polymerization.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221116
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  • 194
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    A study of the mechanism of photocrosslinking polymers by quinones (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2973-2981 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photocrosslinking of poly(methyl methacrylate) (PMMA) was studied in the solid state in the presence of various quinones. For the study of photocrosslinking mechanism, a PMMA film containing p-benzoquinone (Q) was irradiated with UV light (λ 〉 370nm) and then purified by reprecipitation. It was found that the reprecipitated polymer has quinone-type moieties, besides the hydroquinone-type moieties, chemically bound to the polymer chain. The reprecipitated polymer film also crosslinking efficiency was higher than that of PMMA film containing Q. It was concluded that the formation of quinone-type structure during irradiation played an important role in the photocrossing of PMMA containing Q.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221120
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  • 195
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    Electronic Resource
    Ethynyl-terminated polyarylates: Synthesis and characterization (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3011-3025 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydroxy-terminated polyarylates (HTPA) with number-average molecular weights of approximately 2500, 5000, 7500, and 10,000 were synthesized and converted to corresponding 4-ethynylbenzolyloxy-terminated polyarylates (ETPA) by reaction with 4-ethynylbenzoyl chloride. The terminal ethynyl groups were thermally reacted to provide chain extension and crosslinking. The cured ETPA exhibited higher glass transition temperatures (Tg) and better solvent resistance than a high molecular weight linear polyarylate. Solvent resistance was further improved by curing 2,2-bis(4-ethynylbenzoyloxy-4′-phenyl) propane, a coreactant, with ETPA at concentrations of approximately 10% (w/w).
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221124
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  • 196
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    Thermal stability of the silica-aminopropylsilane-polyimide interface (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3043-3062 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermal degradation of the silica-aminopropylsilane-amic acid/imide interface was studied by modifying a high-surface-area, neutral silica gel with a number of substituted aminopropylsilanes (APS). These substrates were reacted further with phthalic anhydride or aromatic amic acid monomers and the thermal decomposition of the adsorbed/reacted materials was monitored by thermogravimetric analysis (TGA) and infrared (IR) spectroscopy. The 3-aminopropyltriethoxysilane/poly[N,N′-(p,p′-oxydiphenylene)pyromellitimide] interface was also evaluated by this method.Comparison clearly distinguishes the thermal decomposition of surface-bound APS from surface-bound alkylphthalimides, the adhesion product of alkylamines and aromatic amic acids. Alkylamine imidization with the elimination of aromatic amine (analogous to polymer scission) and the decomposition of the surface-bound imide are shown in the amic acid TGA profiles. This imidization and the accompanying aniline elimination begin at about 130°C, under nitrogen, to form the surface alkyl imide which slowly decomposes at 400°C. TGA analysis indicates that the surface-bound imide undergoes minimal degradation under nitrogen at 370 ± 10°C; temperatures above this threshold range produce changes in the APS-imide interface.
    Additional Material: 21 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221126
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  • 197
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    Studies of phosphazenes. XIX. New polyorganophosphazenes derived from the friedel-crafts reactions of hexa(aryloxy)cyclotriphosphazenes with polyhaloalkanesFor Part XVIII, see Ref. 1 (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3115-3128 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of hexa(aryloxy)cyclotriphosphazenes N3P3(OR)6[R = C6H5, C6H4CH3-p] with polyhaloalkanes in the presence of anhydrous aluminium chloride yield new crosslinked phosphazene polymers which are characterized by elemental analysis, IR spectroscopy, and pyrolysis - mass spectrometric measurements. Soluble “prepolymers” are obtained by using stoichiometric quantities of the phosphazene and haloalkane in nitromethane as the solvent. The 1H and 31P NMR data for these “prepolymers” are presented. The thermal stability of the polymers derived from various haloalkanes decreases in the order 1,2-ClCH2CH2Cl 〈 CHCl3 〉 CH2Cl2 〉 CCl4. The thermal stability also increases with increasing amounts of the catalyst, reaching a maximum at 1:10 mol ratio of N3P3(OPh)6:AlCl3. The phosphazene polymers reported here possess much greater thermal stability compared to linear polyorganophosphazenes, [NPR2]n, as well as the polymers prepared by the Friedel-Crafts reactions of P(O)(OPh)3 and P(O)(OC6H4CH3-p)3 with haloalkanes.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221131
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  • 198
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    Chemistry of alkenyl azlactones. IV. Preparation and properties of telechelic acrylamides derived from amine-terminated oligomers (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3149-3160 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ring-opening, nucleophilic addition of amine-terminated oligomers to alkenyl azlactones was exploited to prepare reactive, that is, in free radical polymerizations, oligomers that could be used in 100% solids resin systems. Acrylamide-functional oligomers resulted from the reaction that used 2-vinyl-4,4-dimethylazlactone, whereas methacrylamide-functional oligomers were produced with 2-isopropenyl-4,4-dimethylazlactone. The overall reaction took place under mild conditions, for example, a few hours at room temperature, and was particularly free of side reactions. Examination of reaction rates with the two alkenyl azlactones revealed that the 2-vinyl derivative reacted ca. four times faster. The (meth)acrylamide-terminated resins were characterized by IR, NMR, and molecular weight analyses.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170221134
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  • 199
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    Monte carlo study of star-branched polymers on the tetrahedral lattice. II. Statistical thermodynamics of single macromolecules (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 97-106 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermodynamical properties of the star-branched polymers on the tetrahedral lattice are studied taking into account nearest-neighbor interactions. The excess free energy and energy and heat capacities are computed for wide ranges of chain lengths, reduced potential ∊/kT, and number of branches. A significant influence of the degree of branching on long-range interactions in the polymer random coil is observed. The possibilities of phase transitions in both linear and branched systems are discussed on the basis of the Monte Carlo data.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220110
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  • 200
    Electronic Resource
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    Photoinduced swelling control of amphiphilic azoaromatic polymer membrane (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 121-128 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To control the swelling of polymer membrane by photoirradiation amphiphilic azoaromatic polymer membranes were prepared and a photoinduced change in the swelling degree of water was investigated. The azobenzene moiety in the side chain of the polymer was isomerized from trans form to cis form by ultraviolet (UV) irradiation and reverse isomerization was found by visible light irradiation. The swelling degree of the polymer membrane for water in the dark was decreased by UV radiation, and when visible light irradiation was carried out in the polymer membrane the degree of swelling recovered to the original level. The swelling degree decreased with an increase in the mole fraction of the azobenzene moiety in the dark and under UV irradiation. The deswelling degree of the polymer membrane by UV irradiation also decreased with an increase in the mole fraction of the azobenzene moiety. This reversible change in the swelling degree was considered to be caused by the photoisomerization of the azobenzene moiety in the polymer membrane.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220112
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