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  • Physics  (1,093)
  • 1980-1984  (1,093)
  • 1984  (555)
  • 1983  (538)
  • 101
    Electronic Resource
    Electronic Resource
    Degradation of PVCs obtained by controlled chemical dehydrochlorination (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2177-2188 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermal and thermo-oxidative degradation of poly(vinyl chloride)s (PVCs) containing increased concentrations of allylic chlorines, PVC(A)s, prepared by controlled chemical dehydrochlorination with potassium-t-butoxide (t-BuOK) have been studied. The introduction of small amounts of internal allylic chlorines into PVC significantly decreases the thermal and thermo-oxidative stability of the resin. A linear relationship exists between the initial rates (VHCl)0 of thermal and thermooxidative dehydrochlorination of solid PVC(A)s and the concentration S of internal allylic chlorines. Both the slope and the intercept of the thermo-oxidative (VHCl)0 vs. S plot are higher in oxygen than those obtained in nitrogen at the same temperature; this finding is attributed to fast oxidation of polyenes, and to peroxy radicals formed during polyene oxidation, which initiate subsequent HCl loss by attacking normal repeat units in PVC. The extent of HCl loss as a function of time during thermal degradation of PVC(A)s in intert solvent shows a rapid initial phase followed by a slower stationary phase. The first phase is due to dehydrochlorination involving the labile chlorines, while the stationary phase indicates random initiation of HCl loss at normal—CH2—CHCl— repeat units. Initial rates of HCl loss increase with S, while the rates of HCl loss during the stationary phase are independent of S. The rate constant of initiation of HCl loss at internal allylic chlorines is almost four orders of magnitude higher than that of random initiation; however, the former is still orders of magnitude lower than that of chain propagation. Quantitative analysis of UV-visible spectra of PVC(A)s degraded in solution suggests geometric polyene distribution. The average length of polyenes decreases as the extent of HCl loss increases and reaches a constant value of ca. 3 at ca. 1% HCl loss for all the investigated PVC(A) samples.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.170210802
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  • 102
    Electronic Resource
    Electronic Resource
    Comparative recalculation of the monomer reactivity ratios in copolymerization for styrene and methyl methacrylate (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2215-2224 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The monomer reactivity ratios (MMRs) in radical copolymerization for styrene and methyl methacrylate were recalculated by five different methods using literature copolymerization data. The use of approximate 95% confidence limits and their visual inspection helps to separate possibly biased copolymer composition data. The recalculated mean MRR values were r1 (styrene) = 0.501 ± 0.031 and r2 = 0.472 ± 0.031. The results of the linear least-squares calculation procedures seldom approach the quality of the nonlinear least-squares analysis according to the method of Tidwell and Mortimer.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.170210806
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  • 103
    Electronic Resource
    Electronic Resource
    Synthesis of stereoregular heteropolysaccharides having amino-groups by ring-opening copolymerization of 1,6-anhydro-azido-sugar derivatives (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2203-2214 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cationic, ring-opening copolymerization of 1,6-anhydro-2-azido-3,4-di-0-benzyl-2-deoxy-(2-ABG), -3-azido-2,4-di-0-benzyl-3-deoxy- (3-ABG), -4-azido-2,3-di-0-benzyl-4-deoxy-β-D-glucopyranose (4-ABG) with 1,6-anhydro-2,3,4-tri-0-benzyl-β-D-glucopyranose (LGTBE) was investigated with phosphorus pentafluoride as catalyst at low temperatures, giving highly stereoregular, (1→6)-α-linked copolymers with number-average molecular weights of 3.90 × 104-9.27 × 104. Structure and composition of the copolymers were determined by 1H- and 13C-NMR spectroscopies and elemental analysis, which indicated that copolymerization occurred in a stereoregular manner to give azido groups containing (1→6)-α-linked glucopyranan derivatives. The differences in polymerizability among the three azido monomers are discussed. Regioselective reduction of three kinds of heteropolysacharide derivatives which had different quantities of azido groups at C-2, -3, or -4 position with lithium aluminum hydride and subsequent debenzylation of the copolymers with sodium in liquid ammonia produced amino-group-containing heteropolysaccharides.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.170210805
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  • 104
    Electronic Resource
    Electronic Resource
    Coordination polymers. XV. Influence of diols on the reaction between unsaturated polyesters and Mg ionsAuthor proofs received May 10, 1983 (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2225-2236 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An increase in viscosity of reaction mixtures of low molecular mass, COOH, and alcoholic OH-terminated polyesters with MgO is considerably reduced by the presence of diols in the system. This effect is analogous with that described for the presence of water. Joint presence of water and diol results in an additive effect. The mechanism of this effect can be interpreted by coordination chemistry. In this system both diol and water saturate the coordination sphere of Mg2+ ion (as ligands). Consequently, the coordination of donor groups of polyester (terminal OH and ester carbonyl groups) is suppressed by reducing the extent of linking the polyester molecules with coordination bonds; that is, the average molecular mass of the system. Moreover, coordination of low-molecular ligands modifies the final molecular structure that occurs in the system. In addition, some kinetic effects are revealed in the process because the system is diffusion-controlled by the ever-increasing viscosity. This effect is also favorable to the coordination of low molecular mass ligands. All of these factors lead to a reduction in the increase of viscosity in the present system.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.170210807
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  • 105
    Electronic Resource
    Electronic Resource
    Preparation of polystyrene labeled with amino groups at specific sitesNCRR No. 21151. (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2237-2240 
    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 monodisperse polystyrene substituted with single dimethylamino groups is described. Three methods are adopted. The first involves the use of a dimethylamino-substituted initiator to give an end amino group. The second uses an ester coupling reaction with a dimethylamino-substituted methyl valeric ester to give a central amino substituent. The third method, which is capable of giving an amino substituent at any selected place along the chain, uses a dimethyl-amino-substituted butadiene derivative as a comonomer in a sequential polymerization. This latter method takes advantage of the unusual reactivity ratios of styrene and dienes in anionic copolymerization.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.170210808
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  • 106
    Electronic Resource
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    ESR study of free radicals produced from the reaction of o-substituted phenyl methacrylates with tert-butoxy radical (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2241-2247 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ESR spectra of radicals produced from the reactions of phenyl methacrylate (PMA) and four o-substituted PMAs, 2,4,6-trimethyl-, 2,6-diisopropyl-, 2,6-di-tert-butyl-, and 2,6-di-tert-butyl-4-methyl-PMAs, with tert-butyoxy radical were measured in 2-methyltetrahydrofuran over the temperature range of -53 to -15°C. The coupling constants of the β-methylene protons observed varied with the bulkiness of the o-substituents, whereas the p-substitution did not affect the pattern of the spectra. 2,6-Diisopropyl- and 2,4,6-timethyl-PMAs, which can form homopolymers, gave 5- and 13-line spectra, respectively. For the radicals from 2,6-di-tert-butyl- and 2,6-di-tert-butyl-4-methyl-PMAs, the same 8-line spectrum was observed, indicating that the coupling constant of one of the β-methylene protons was too small to detect. Conformations of the radicals were deduced from the coupling constants of the β-methylene protons. Variation of the ESR spectrum according to the bulkiness of the o-substituent was interpreted as a consequence of steric interactions between the polymer chain bound to the β carbon and the substituents, and the α-methyl group.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.170210809
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  • 107
    Electronic Resource
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    Liquid-crystalline copolyesters based on poly(p-oxybenzoate) and poly(p,p-biphenylene terephthalate) (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2249-2259 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two copolymers composed of p-hydroxybenzoate (PHB) and biphenylene terephthalate (BPT) with PHB/BPT ratios of 1/2 and 2/1 were characterized with respect to their tendency to exhibit liquid-crystalline behavior in the melt phase. The BPT -rich copolyester, PHB/BPT = 1/2, displayed a birefringent melt phase of very high viscosity and no tendency to crystallize on cooling. The resulting fused material exhibited what apeared to be a second-order transition at 170°C. The PHB-rich composition, PHB/BPT = 2/1, also exhibited a highly birefringent melt phase of high viscosity which was quite shear sensitive. This polymer melt had little tendency to crystallize on cooling; however, on reheating no apparent second-order transition could be detected. The observed phase changes were characterized by differential scanning calorimetry, hot-stage microscopy, and wide-angle x-ray diffraction techniques. Additional data, pertaining to the compositional nature and apparent sequence distribution, were obtained by 13C-NMR spectroscopy of the solid materials through magic-angle spinning, dipolar decoupling, and cross-polarization techniques.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.170210810
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  • 108
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    Copolymerization of acrylonitrile with 3-chloro, 2-hydroxy-propyl acrylate and methacrylate (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2261-2270 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acrylonitrile (AN) was copolymerized with 3-chloro, 2-hydroxy propyl acrylate (CHPA) and 3-chloro, 2-hydroxy-propyl methacrylate (CHPMA) in water and water-acetone medium at 40°C with potassium persulfate and sodium metabisulfite as redox initiators. Copolymer composition was determined from the nitrogen content. The reactivity ratios for the AN-CHPMA system were also calculated by the Kelen-Tudos method. The reactivity ratio r2 (CHPMA) was higher for the AN-CHPMA system in both media, which indicated higher reactivity of CHPMA toward the propagation species. Addition of acetone decreases r2 and increases r1. It was found that the copolymers prepared in water medium were not completely soluble in dimethylformamide (DMF); the insoluble fraction was rich in CHPA/CHPMA and increased with increasing comonomer composition. The influence of the acrylate comonomer on properties such as solubility and intrinsic viscosity was also studied.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.170210811
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  • 109
    Electronic Resource
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    Effect of active-group position in polymeric interactions (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2271-2276 
    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 the position of a substituent along a polymer chain on the equilibrium constant in interpolymer interactions has been determined for equilibria involving the substituent. Polymers containing single dimethylamino groups have been equilibrated with coupling bidentate dinitro phenols, and the excluded-volume effect determined. The magnitude of the hindrance to complex formation was found to be considerably greater for centrally substituted polymers than for end-substituted polymers. However, for all polymers the measured effect is less than those expected from previous theoretical treatments of interpolymer reactions. Also, the size of the effect is less in the equilibria than found previously for interpolymer reactions. This suggests that the theoretical treatments that deal only with the effect of excluded volume on the transition complex may be oversimplifications.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.170210812
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  • 110
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    Synthesis and characterization of polyesters derived from aromatic 1,4-dimethoxylated diacids (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2277-2281 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyesters were synthesized from the dichlorides of 2,5-dimethoxyterephthalic and 2,5-dimethoxy-1,4-benzenediacetic with dialcohols. The polymers were characterized by elemental analysis and infrared (IR) spectroscopy. Their intrinsic viscosity, glass transition temperature, and thermal decomposition were determined.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.170210813
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  • 111
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    New polymer synthesis. IX.Part VIII: H. R. Kricheldorf and J. M. Jonté, Polym. Bull., 9, 276 (1983). Synthesis of poly(ether sulfone)s from silylated diphenols or hydroxybenzoic acids (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2283-2289 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The condensation polymerizations of bis(4-flurophenyl) sulfone with the bistrimethylsilyl derivates of bisphenol-A, 4,4′-dihydroxydiphenyl sulfone, 1,5′-dihydroxynaphthalene, 3-hydroxybenzoic acid, and 4-hydroxybenzoic acid were investigated. These polycondensations were only successful when potassium or cesium fluoride was used as catalyst. The yields were in the range of 91-98% and the number molecular weights in the range of 2,500-17,500 depending on the reaction conditions. Viscosity and GPC measurements were conducted and glass transitions were determined. Crystallization was never observed.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.170210814
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  • 112
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    Synthesis and characterization of certain aromatic polyfumaramides (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2301-2309 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ten polyfumaramides based on p,p′-aromatic diamines and fumaric acid were synthesized by the phosphorylation method. The polymers were characterized by viscosity, solubility, infrared and UV-visible spectroscopy, and thermogravimetry. The fluorescence spectra of one of the polymers were studied. A model compound, fumaroyldianilide, was synthesized and characterized.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.170210816
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  • 113
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    Study of photopolymer. XIX. Novel syntheses of the polymers with pendant ester and chloromethyl groups by addition reactions of the copolymer of glycidyl methacrylate with acid chlorides (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2291-2299 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymer with pendant cinnamic ester and chloromethyl groups was synthesized by the addition reaction of poly(glycidyl methacrylate-co-methyl methacrylate) (PGMA) with cinnamoyl chloride. Also, polymers with pendant benzoic esters and chloromethyl groups were synthesized by reaction of PGMA with the corresponding benzoyl chlorides. Furthermore, polymers with cinnamic or benzoic esters and alkylazide groups were prepared by the substitution reaction of the obtained polymers with sodium azide.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.170210815
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  • 114
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    Interaction of crosslinked polyethylenimine with a homologous series of methyl orange derivatives in aqueous solution (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2311-2322 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyethylenimine (PEI) was crosslinked with dichloroethane, glyoxal, or glutaraldehyde and polymers of various degrees of crosslinkage were made. The insoluble polymers obtained were examined for their ability to bind methyl orange and its homologs, methyl, ethyl, propyl, and butyl orange at 5, 15, 25, and 35°C, respectively, in an aqueous solution. PEI crosslinked with glutaraldehyde showed markedly increased binding affinity toward these cosolutes compared with the polymers crosslinked with dichloroethane or glyoxal. The extent of the binding increased with an increase in the degree of crosslinkage. These results suggest that the enhancement of the binding by the crosslinking is due mainly to a dual effect, introduction of hydrophobic moieties and proximity of neighboring polymer chains. The first binding constants and the thermodynamic parameters that accompanied the binding were calculated. The thermodynamic data show that the binding process is athermal and is stabilized entirely by the entropy term. Water-soluble PEI exhibited stronger cooperative interactions than the crosslinked polymer because the mobilities of the chains of the former are greater than those of the latter.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.170210817
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  • 115
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    Ignition of poly(methyl methacrylate) slabs using a small flame (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2323-2334 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When exposed to a lean hydrogen-oxygen flat flame, slabs of poly(methyl methacrylate) ignited to flaming combustion after a delay, the length of which depended on the gas temperature and the separation between the slab and the igniting flame. The delay obeyed an Arrhenius-type expression, giving an activation energy of 96 ± 8 kJ mol-1. By the end of the delay the surface of the sample was pitted if the delay was long and almost unchanged if the delay was short. The rates of flame development measured immediately after the ignition were proportional to the ignition delay, the proportionality constant varying with the separation between slab and flame. These rates decreased as temperature increased; the slope of the linear Arrhenius plots was independent of slab-flame separation. During the delay, carbon dioxide was formed within the boundry layer and a blue preignition glow was visible at its outer edge. These data were explained by a model in which ignition delay is governed by the induction period of gas-phase reactions in or near the boundry layer. Models in which delay is governed by the time taken to heat the polymer to a critical ignition temperature did not satisfactorily explain the data.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.170210818
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  • 116
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    Preparation and photolysis of polyamides having coumarin dimer component (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2345-2362 
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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 ring-opening polyaddition reaction of anti and syn head-to-head Coumarin dimers with diamines and the photocleavage behavior of the resulting polyamides were investigated. Anti head-to-head Coumarin dimer successfully reacted with aliphatic and aromatic diamines in an aprotic polar solvent to give corresponding high molecular weight polyamides. The polyamides showed good film forming ability and exhibited solubility behavior typical of polyelectrolytes. Furthermore, these polyamides were found to undergo exclusively asymmetric photocleavage on the cyclobutane rings in the polymer main chain to give a fumaramide unit with elimination of 2,2′-dihydroxystilbene. On the other hand, syn head-to-head Coumarin dimer gave only low molecular weight polyamides. These polymerization and photocleavage behaviors were elucidated in comparison with those of model reactions.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.170210820
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  • 117
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    Comparisons of glow discharge polymerization between hexamethyldisilazane and trimethylsilyldimethylamine (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2335-2343 
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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 polymerization between hexamethyldisilazane (HMDSZ) and trimethylsilyldimethylamine (TMSDMA) was compared by means of infrared spectroscopy and ESCA analysis. Infrared spectra pointed out differences in chemical structure between the polymers prepared from the two monomers, although the two polymers were mainly composed of resembling units such as Si—CH3, Si—CH2, Si—H, Si—O—Si, and Si—O—C groups: (i) The polymers prepared from TMSDMA contained N → O group, but the polymers from HMDSZ did not contain this group. (ii) Influences of the W/FM parameter (W is the input energy of rf power, F the flow rate of the monomer, and M the molecular weight of the monomer) appeared on decreasing the C—N group and increasing the C=O group in the TMSDMA system, but little influence appeared in the HMDSZ system. ESCA spectra (C1s, Si2p, and N1s core levels) supported the differences between the two polymers elucidated by infrared spectroscopy, and pointed out differences in susceptibility of the Si—N bond to plasma: The N—Si sequence of TMSDMA was completely ruptured in discharge to yield polymers, and the Si—NH—Si sequence of HMDSZ remained in considerable amount.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.170210819
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  • 118
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    Free-radical identification by ESR in polyethylene and nylon (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2405-2425 
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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: Identification of the free radicals in polyethylene and nylon produced by irradiation, grinding, and pulling to fracture was carried out by comparing the experimentally observed spectra with the spectra constructed from theoretical consideration with the aid of a computer. It was demonstrated that the various primary and secondary radicals are produced and formed in the materials depending upon means of degradation, degradation processes, orientation of materials, and conditions of ESR measurement.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1983.170210824
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  • 119
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    Batch and semicontinuous emulsion copolymerization of vinyl acetat-butyl acrylate. I. Bulk, surface, and colloidal properties of copolymer latexes (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2363-2382 
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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: Vinyl acetate (VAc)-butyl acrylate (BuA) comonomer mixtures with various composition were polymerized by batch and semicontinuous emulsion polymerization processes. PVAc and PBuA homopolymer latexes as well as the (VAc-BuA) copolymer latexes were characterized with respect to particle size, molecular weight, acid end groups on particle surfaces, and colloidal stability against electrolytes. The surface and colloidal properties of these latexes were also compared before and after aging and acid hydrolysis. The average particle size of batch latexes was independent of copolymer composition, whereas for semicontinuous latexes it decreased with increasing BuA content and was always lower than that of the corresponding batch latex. The molecular weight distribution (MWD) for batch latexes was narrower and much less dependent on composition than that of the semicontinuous latexes; bimodal MWD was found in most semicontinuous latexes with a substantial amount of low MW fraction. The total weak and strong acid end groups on particle surfaces for semicontinuous latexes is higher, and more dependent on composition, than the batch latexes. Acid-induced hydrolysis results in a drastic change in the type and concentration of the surface groups of the semicontinuous latex particles. Colloidal stability against electrolytes showed that both electrostatic (due to surface acid groups) and steric [due to surface poly(vinyl alcohol)] mechanisms are contributing. However, for semicontinuous latexes, increasing PVAc content above 50 mol % resulted in a proportional increase and ultimately dominant role of steric stabilization. The results were interpreted in terms of differences in reactivity ratios and water solubilities of the two monomers and their effects on the locus of initiation and growth in the two polymerization processes, as well as the monomer sequence within the polymer chain and degree of homogeniety of the copolymer composition within the particle.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1983.170210821
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  • 120
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    Intrinsic reactivity of active species in Ziegler-Natta polymerization of ethylene initiated with Li/Ti-based macromolecular complexes (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 3877-3884 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of ethylene was initiated with soluble polystyrene100-butadiene3-Li/TiCI4 complexes in toluene leading to block copolymers. The activity of the system was measured at a constant ratio r = [Li]/[Ti] and for different concentrations in active centers and in monomer. Measurement of the amount of the block copolymers formed led to the direct determination of the efficiency of the catalytic system. This efficiency is defined with respect to the number of potentially active centers and is close to 90%. From both measured values of activity of the catalytic system and of its efficiency, the rate constants of propagation were deduced. The kinetic behavior of the system is fully consistent with that of a living system. The rate is first order towards both ethylene and active centers concentrations. So, the rate constant of propagation is an absolute rate constant, measuring the intrinsic reactivity of active sites. Determination of the absolute rate constant at different temperatures, led to thermodynamic parameters of the propagation reaction. The chemical composition of the complex and the absence of polymeric aggregation, leads to propose a structure of the active species: a bioctahedral binuclear structure is consistent with kinetic, thermodynamic results, and structural determinations.
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    Aqueous polymerization of methyl methacrylate. III (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2665-2674 
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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 aqueous polymerization of methyl methacrylate (MMA) initiated by potassium persulfate (I)-thiomalic acid (TMA) redox couple has been studied at 30 ± 0.2°C under nitrogen atmosphere. The rate of polymerization is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ R_p = K[{\rm MMA}]^{0.98} [{\rm K}_2 {\rm S}_2 {\rm O}_8]^x [{\rm TMA}]^{0.44} $$\end{document} up to 20.0 mmol/L TMA concentration, where x = 0.52 for the I concentration 0.6-10 mmol/L and x = 0.27 for higher I concentrations. The temperature had a marked effect on initial rate and maximum conversion. The overall energy of activation was found to be 11.79 kcal/mol (49.31 kJ/mol). Injection of more initiator (I) at intermediate stages enhanced both the initial rate and maximum conversion. Ag (I) and Fe (III) depressed initial rate as well as maximum conversion, while Cu (II) activated the polymerization. The effect of solvent was also studied.
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    Etude par RMN 13C à 62,89 MHz de ramifications longues d'alcanes lourds branchés. Modèles de PEbd et des copolymères éthylène-α oléfines (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2755-2762 
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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 12-alkyl tricosanes (four compounds) was examined by use of 13C nuclear magnetic resonance at 62,89 MHz as model compounds for isolated short- and long-chain (C5, C6, C7, C8) branches in low-density polyethylene and ethylene-α olefin copolymers. An array of 13C resonances was observed and we note that the 13C chemical shifts became insensitive to branch length with octyl and longer branches at this field.
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    Radical polymerization in the presence of complexing agents. VI. Effect of low concentrations of ZnCl2 on the overall rate of copolymerization of methyl methacrylate with ethyl acrylate (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2749-2754 
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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: Overall rates for the free-radical copolymerization of methyl methacrylate with ethyl acrylate in the presence of low concentrations of ZnCl2 have been determined at 50°C. The rate of copolymerization Rp depends on both the ZnCl2 concentration and the monomer feed composition. Relative copolymerization rates Rp/R0p where R0p is the rate of copolymerization in the absence of complexing agent in the reaction mixture, show a minimum for intermediate feed compositions, independently of the ZnCl2 concentration. On the basis of the results obtained, a conventional copolymerization mechanism is proposed for this system in which free and complexed species of both acrylic monomers participate.
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    Synthesis of poly(vinyl alcohol)-based poly(crown ether)s and permeability of their polymeric membranes (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2777-2785 
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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: Polymers that contain crown ether moieties at the side chain and are capable of forming rather tough film were synthesized by the polymer reaction of poly(vinyl alcohol) with formyl derivatives of aliphatic crown ethers such as 12-crown-4, 15-crown-5, and 18-crown-6. In the passive transport of alkali metal picrates across the poly(crown ether) membranes the permeation, particularly of alkali metals which tend to form intramolecular sandwich-type complexes with the crown ether rings, was retarded, compared with a poly(vinyl alcohol) membrane. The cation selectivities in the permeation of poly(crown ether) membranes differed significantly from those of poly(vinyl alcohol).
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    The effect of filler shape on the mechanical properties of a reinforced vulcanizate: The SBR-ground asbestos system (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2833-2836 
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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: Grinding chrysotile under controlled conditions results in microfibers with the dimensions of carbon black or silica agglomerates used in the reinforcement of rubber. The mechanical properties of SBR reinforced with ground asbestos are similar to those of SBR filled with a silica of equivalent surface area.
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    Preparation of polyamides via the phosphorylation reaction. VII. Synthesis of polyoxamides and regular copolyoxamides (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2837-2841 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1983.170210919
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    Erratum (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2843-2843 
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    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.1983.170210920
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    Vinyl polymerization. 416. Polymerization of vinyl monomer initiated by polyethyleneglycol (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2897-2906 
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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 polymerization of vinyl monomer initiated by polyethyleneglycol (PEG) in aqueous solution was carried out at 85°C with shaking. Acrylonitrile (AN), methyl methacrylate (MMA), and methacrylic acid were polymerized by PEG-300 (M̄n = 300), whereas styrene was not. The effects of the amounts of monomer and PEG, the molecular weight of PEG, and the hydrophobic group at the end of PEG molecule on the polymerization were studied. The selectivity of vinyl monomer and the effect of the hydrophobic group are discussed according to “the concept of hard and soft hydrophobic areas and monomers.” The kinetics of the polymerization was investigated. The overall activation energy in the polymerization of AN was estimated as 37.9 kJ mol-1. The polymerization was effected by a radical mechanism.
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    Plasma polymerization. IX. A systematic investigation of materials synthesized in inductively coupled plasmas excited in perfluoropyridine (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2907-2919 
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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 RF plasma polymerization of perfluoropyridine was investigated for a range of operating parameters. The stoichiometries of the resulting thin films indicated a predominance of rearrangement mechanisms in their formation in which both nitrogen and fluorine were retained at approximately the same level as in the starting monomer. In appropriate cases a comparison was drawn with plasma polymers produced under comparable conditions from perfluoro and pentafluorobenzenes. Although the plasma polymer films from the benzenes have a low critical surface tension, that for the pyridine system changes with time, and the surface becomes completely wettable with water. This is attributed to surface hydrolysis of the plasma polymer films produced from perfluoropyridine.
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    The analysis of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO® resin) in mixtures of PPO resin, polystyrene, and copolymers of PPO resin and polystyrene (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2921-2936 
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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 method of determining the quantity of ungrafted poly(2,6-dimethyl-1,4-phenylene oxide) (PPO®Trademark of General Electric Company. resin) in mixtures of such polyphenylene oxide or PPO resin, polystyrene (PS), and graft copolymers of PPO resin and PS is described. The technique is a combination of physical and chemical separations and gel permeation chromatographic (GPC) analysis. The extent of grafting on PPO resin and the quantity of ungrafted PPO resin were calculated from molecular weight data and compositional analysis.
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    The investigation of cancerous human bone (osteoclastoma) by small-angle X-ray scattering (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2937-2944 
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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: Small-angle X-ray scattering methods were applied to provide a pore analysis of cancerous human bone (osteoclastoma). For experimental measurements of the scattering intensities a small-angle Kratky camera, equipped with a counterattachment and a programmable step-scanning device, was used. By applying the theories of Kratky, Porod, Debye, and Bueche, applicable to a densely packed two-phase system belonging to a general micelle system, macromolecular parameters such as specific inner surface, length of coherence, range of inhomogeneity, void percentage, and transversal lengths l̄1 and l̄2 were evaluated and found to be 4.69 × 10-4 Å-1, 21.39 Å, 18.01 Å, 0.21%, 18.01 Å and 8.53 × 103 Å, respectively. A comparison of these parameters with those of pure human bone revealed a macromolecular dissociation in osteoclastoma.
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    Comments on a kinetic approach of multifunctional polycondensation and gelation by J. W. Stafford (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2945-2946 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/pol.1983.170211009
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    Reply to the comments of professor D. Durand et al.See D. Durand, M. Riviere, and C. M. Bruneau, J. Polym. Sci. Polym. Chem. Ed., 21, 2945 (1983). (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2947-2948 
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    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.1983.170211010
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    Preparation of monodisperse reactive styrene-glycidyl methacrylate latexes by the emulsifier-free dispersion copolymerization technique (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2949-2960 
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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: Latexes based on styrene-glycidyl methacrylate copolymers were prepared by the emulsifier-free dispersion copolymerization technique. The main factors affecting the size and morphology of the latex particles and their distribution are the initiator concentration (K2S2O8), the total ionic strength of the aqueous phase, and the total monomer concentration. The existence of critical values for these variables was demonstrated. In the range in which these factors had values below the critical, the synthesized latex particles were spherical, homogeneous, and in varied sizes, depending on the abovementioned parameters in the range of 220-500 nm. Above the critical values of these variables the latex particles consisted of spherical aggregates of smaller particles. The reactive oxirane groups of the latex particles were modified later by hydrolysis, ammonolysis, reaction with Na2S, or periodic acid oxidation of the hydrolyzed or ammonolyzed forms of the latex particles.
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    Linear polythioesters. VI.For Part V of this article see ref. 7. Products of interfacial polycondensation of bis/4-mercaptophenyl/ether with some aliphatic acid dichlorides (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2961-2972 
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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 bis/4-mercaptophenyl/ether with oxalyl, succinyl, adipoyl, suberoyl, or sebacoyl chlorides were obtained. To define the optimal conditions of the process, the polythioesters of dithiol and adipoyl or sebacoyl chlorides were chosen as a model system. Yield for all reaction products and reduced viscosity were found. The following factors were studied: organic phase, contribution of catalyst, concentration and molar ratio of reagents, rate of addition of acid chloride, temperature of reaction, contribution of emulsifier, and concentration of hydrochloride acceptor. The structure of all polythioesters was determined by elementary analysis, infrared spectra, and x-ray. Initial decomposition and initial intensive decomposition temperature were defined by the curves of thermogravimetric analysis. Some mechanical and electrical properties of polythioesters from dithiol and adipoyl or sebacoyl chlorides were studied. The molecular weights for these polymers were also determined by gel-chromatography.
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    Synthesis, characterization, and Diels-Alder extension of cyclopentadiene telechelic polyisobutylene. III. Silylcyclopentadiene-telechelic polyisobutylenePart XXXIII of the series “New Telechelic Polymers and Sequential Copolymers by Polyfunctional Initiator-Transfer Agents (Inifers)”.Parts of this article have been presented at the National Meeting of the American Chemical Society, Kansas City, September 12-17, 1982. (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2973-2986 
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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: Telechelic polyisobutylenes with silylcyclopentadiene termini (CpSi-PIB-SiCp) were prepared, starting with α,ω-di(t-chloro)polyisobutylene and followed by dehydrochlorination, hydrosilylation, and cyclopentadienylation. The prepolymer was characterized and found to have a terminal functionality close to 2.0. Thermal chain extension by Diels-Alder addition of the end groups did not occur, most likely because of fluxional isomerization of the silylcyclopentadiene end groups, confirmed by model studies. Chain coupling of CpSi-PIB-SiCp prepolymers with stoichiometric amounts of bismaleimide gave rise to degrees of extension of more than 11.
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    Structure and sorption properties of the polyion complex between poly(acrylic acid) and poly(4-vinylpyridine) (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2987-2995 
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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 polyion complex was formed from poly(acrylic acid) (PAA) and poly(4-vinylpyridine) (PVP). Its structure and composition were examined by means of infrared spectroscopy (IR), x-ray photoelectron spectroscopy (XPS), and elemental analysis. The polyion complex was obtained by dissolving PAA and PVP together in methanol. The composition of the polyion complex was independent of stirring speed, mixing sequence, and standing time after mixing. However, the composition depended on the concentrations and the ratio of the components in the reaction mixture. Excess of PAA in the product was observed when concentrated solutions (2.0 × 10-1M) were used for the preparation or when an excess of PAA was added to PVP. The sorption of water vapor by an equimolar PAA/PVP complex at 293 and 303 K was higher than that by the pure components, especially in the low- and middle-pressure regions. In the high-pressure region, however, the uptake was not affected by the complex formation. While hydrogen bond interactions in general decrease sorption, Coulombic interactions between polymer chains increased the sorption capacity.
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    Radical-initiated homo- and copolymerization of cyanomethyl methacrylate (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 2997-3008 
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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 cyanomethyl methacrylate (CyMA) homopolymerization was investigated in acetonitrile with azobisisobutyronitrile as initiator. The rate of polymerization Rp was expressed by Rp = k[AIBN]0.49[CyMA]1.2 and the overall activation energy was calculated as 72.3 kJ/mol. Kinetic constants for CyMA polymerization were obtained as follows: kp/k1/2t = 0.10 L1/2s-1/2; 2fkd = 1.57 × 10-5s-. The relative reactivity ratios of CyMA(M2) copolymerization with styrene (r1 = 0.15, r2 = 0.29) and methyl methacrylate (r1 = 0.43, r2 = 0.75) in acetonitrile were obtained. Applying the Q-e scheme (in styrene copolymerization) led to Q = 1.64 and e = 0.98. The glass transition temperature Tg of poly(CyMA) was observed to be 91°C by thermomechanical analysis. Thermogravimetry of poly(CyMA) showed a 10% weight loss at 265°C in air.
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    Photoconductivity and hole transport in polymers of aromatic amine-containing methacrylates (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3033-3033 
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    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.1983.170211018
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    Novel high-temperature-resistant metal phthalocyanine imide copolymers (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3063-3072 
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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 metal phthalocyanine imide copolymers with high thermal stability, based on the reaction between metal (11) 4,4′,4″,4‴-phthalocyaninetetraamine, 4-aminophenylether, and 1,2,4,5-benzenetetracarboxylic dianhydride, were prepared. Infrared (IR) spectra, thermogravimetric analysis (TGA), and viscosity measurements were used to characterize these polymers. All polymers exhibited good thermal and thermooxidative stability at polymer decomposition temperatures (PDT) greater than 500°C in air and nitrogen atmosphere. Another attractive feature is their high char yields - 60-75% at 800°C in nitrogen atmosphere. The ratio of the polymer decomposition temperatures in air and nitrogen atmospheres, (PDTair)/(PDTN2), varied from 0.94 to 0.98. These polymers have promising applications in heat-stable films, fibers, and coatings.
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    Solid-state polymerization studies of conjugated diacetylenes deca-2,8-diene-4,6-diyne-1,10-diol and derivatives (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3073-3082 
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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 title diacetylenic compound (D3) and its derivatives dibenzoate (D3B), dinitrobenzoate (D3mNB), ditosylate (D3PTS), and diurethane (D3PU) were synthesized and their solid-state reactivity examined under irradiation and thermal stimulation. D3, D3B, and D3PTS crystallized in reactive phases. The thermal and irradiation polymerization behavior of D3 and D3B was examined further by time-conversion curves.
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    Effects of ionizing radiation on linear aromatic polyesters (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3083-3092 
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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 influence of chemical structure on the response of aromatic polyesters to high-energy ionizing radiation was studied. Systematic variations of polymers related to poly(ethylene terephthalate) were subjected to γ radiation, and the competitive chain scission and crosslinking reactions were determined by measuring changes in intrinsic viscosity and molecular weights. It was found that an increase in the paraffinic glycol segment of polyterephthalates facilitated crosslinking, while the protective nature of aromatic groups was demonstrated by modifying the dibasic acid segments. The influence of substituents on the terephthalate moiety was mixed: electronegative groups led to chain scission (as evidenced by decreased viscosities), but electropositive substituents exerted a stabilizing effect on polymer viscosity. In almost all cases, number-average molecular weights were decreased by exposure to γ radiation, regardless of viscosity behavior. Crystalline melting temperatures of the polymers generally were decreased by the combined radiation effects of chain scission and crosslinking.
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    Structure of chlorinated poly(vinyl chloride). XII. Configuration and reactivity of low-molecular-weight models of poly(vinyl chloride) in the course of chlorination (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3093-3100 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chlorination of poly(vinyl chloride) (PVC) was investigated by means of low-molecular-weight models of PVC - a dimer and trimer of PVC, viz., 2,4-dichloropentane (2,4-DCP) and 2,4,6-trichloroheptane (2,4,67-TCH). Chlorinations of stereoisomeric mixtures of 2,4-DCP and 2,4,6-TCH have revealed that the d,1 form of 2,4-DCP (syndio-2,4-DCP) is more reactive in the chlorination than the meso form of 2,4-DCP (iso-2,4-DCP), while in the case of the chlorination of 2,4,6-TCH the reactivity of stereoisomers decreases in the order iso-〉 hetero-〉syndio-2,4,6-TCH; consequently, analogous structures of stereoisomers of 2,4-DCP and 2,4,6-TCH react in a reverse order and not in the same one. The qualitative order of reactivities of stereoisomers may be correlated formally with the magnitude of their dipole moments. The reactivity of stereoisomers of 2,4-DCP and 2,4,6-TCH decreases with increasing dipole moment.
    Additional Material: 4 Tab.
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    Effect of sulfur on the electrical conductivity of FEF-loaded SBR during swelling (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3353-3360 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Following a series of experiments on the effect of different factors of the electrical conductivity of carbon-black-loaded styrene butadiene rubber, an attempt was made to study the effect on electrical conduction of changing the sulfur content. It was found that an optimum sulfur content leads to a swelling-resistant composite with good electrical insulation. This was done for dry as well as wet specimens of rubber.
    Additional Material: 6 Ill.
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    The skewness of polymer molecular weight distributions (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3373-3380 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new parameter α3 for characterization of the skewness of a polymer's molecular weight distribution (MWD) based on the statistics is introduced. For α3 〉 0, the skewness is positive, characterizing the MWD with a tail at higher-MW side. For α3 = 0, the MWD is symmetric. For α3 〈 0, the skewness is negative, characterizing the MWD with a tail at the lower-MW side. A relationship between α3 and the first four (from zeroth to third) moments of the MWD is developed which allows calculation of the skewness without detailed calculation of the MWD. An example of polymerization of styrene with n-butyllithium is given to demonstrate the characteristics of α3.
    Additional Material: 4 Ill.
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    Intumescent flame retardants for polymers. II.For Part I, see ref. 1. The polypropylene-ammonium polyphosphate-polyurea system (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3361-3371 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of action of ammonium polyphosphate (APP) and polyurea (PU) as flame retardant (FR) agents for polypropylene (PP) was examined. The APP-PU system behaves as an intumescent flame-retardant (IFR) formulation. Comparison of the oxygen index (OI) measured on molded pellets and rods, values of the polymer temperature measured just below the burning surface, and visual considerations describe the IFR action of this system. A strong synergism between APP and two of the four polyureas investigated here was ascertained with a maximum 3:1 ratio. Thermogravimetric (TG), OI, nitrous oxide index (NOI), and char-residue measurements were made. On the basis of our data, it can be concluded that polyurea acts as a catalyst for the charring reactions of the APP on PP.
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    Effect of Rh(III) and Ru(II) complexes in the polymerization of vinyl monomers initiated by charge transfer mechanism (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3381-3388 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The initiation of polymerization of vinyl monomers such as methyl methacrylate (MMA) and methyl acrylate (MA) by a charge transfer complex formed between n-butylamine(nBA) and carbon tetrachloride (CCl4) in dimethylsulfoxide (DMSO) at 30°C is slow. The effect of the dimethylsulfoxide complexes of Rh(III) and Ru(II) on the polymerization of MMA and MA in the presence of nBA, and CCl4 in DMSO has been studied. The rate of polymerization and percent conversion of the MMA and MA at 30°C are evaluated at the critical concentration of the metal complexes. At the critical range of the metal complex concentrations, both Rp, and percent conversion of MMA and MA were found to be highest. However, above and below the critical concentrations, Rp and percent conversion of the monomers were found to decrease. A suitable mechanism for the polymerization has been proposed.
    Additional Material: 6 Ill.
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  • 148
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    Spectroscopic investigation of organosilicon polymers. I. Vibrational analysis of poly(tetramethyl-p-silphenylene-siloxane) (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3389-3402 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This article is a detailed, normal coordinate analysis of an isolated chain of poly(tetramethyl-p-silphenylene-siloxane), based on results obtained for the corresponding monomer and a recent x-ray structure. Predicted vibrational frequencies are compared with new experimental infrared (IR) and Raman data obtained from powder and well oriented films. Vibrational spectra were also obtained for a deuterio derivative in which all hydrogens in the benzene rings were replaced with deuterium atoms. The results indicate that an intermode mixing occurs between vibrations of the ring and the saturated part which lead to low frequency normal modes characteristic of the chain. The simplified valence force field obtained for this polymer should provide a useful tool for understanding the vibrational spectra of other members of the class of polysiloxanes.
    Additional Material: 6 Ill.
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  • 149
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    Grafting of living poly(ethylene oxide) onto polystyrene via aromatic nucleophilic displacement of activated nitro groups (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3425-3442 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polystyrene of M̄ω = 2.2 × 104 was alkylated with 4-nitrophthalimidomethyl groups as grafting sites. Several backbone polymers with various degrees of grafting sites (G = 2-100%) were prepared and characterized by elemental analysis, IR, 1H- and 13C-NMR, and viscosity measurements. “Living” poly(ethylene oxide) with narrow molecular-weight distribution was prepared in the presence of 15-crown-5, and grafted onto the 4-nitrophthalimidomethylated polystyrene. The nitro displacement reaction was fast and the grafting yield was quantitative (100%). The graft copolymers are highly soluble in water and in organic solvents. The intrinsic viscosities of the graft copolymers are higher than those of the backbone polymers. The intrinsic viscosities show an initial increase followed by a decrease as the degree of grafting increase.
    Additional Material: 5 Ill.
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  • 150
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    Electron-proton and electron-methyl exchanges in pyrolysis of polyacetylene and polymethylacetylene (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3453-3477 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrolysis of polyacetylene is marked by high yields of proton-enriched products methane, ethane, ethylene, propane, polypylene, butadiene, cyclopentadiene, 1,3-pentadiene, and toluene in total amounts exceeding benzene. The activation energies for their formation are low. Polyacetylene doped with AsF5 and iodine produced these products in even higher yields of two to 17 times of undoped polymers. The dominant mechanism is thought to be random-chain scission followed by electron-proton exchange reactions. Polymethylacetylene is thermally less stable than polyacetylene. Pyrolysis gave mesitylene as the expected main product. However, as in the case of polyacetylene, large amounts of proton-enriched products were formed with moderate activation energies. (The yields of methane, propylene, and propane are nearly the same in the pyrolysis of polymethylacetylene as compared to that of polyacetylene at 923°K referenced to mesitylene and benzene, respectively.) By analogy, mechanisms involving both electron-proton and electron-methyl exchange reactions were proposed to account for the formation of all the pyrolyzates of polymethylacetylene. These reactions, not observed in the pyrolysis of polypropylene and polyisoprene, are attributable to the conjugated backbone permitting facile migrations of electrons, protons, and methyl groups.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1983.170211209
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    Thermal oxidation of polyacetylene (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3479-3492 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal oxidation of undoped trans-polyacetylene powder in dry air has been studied and the principal features of the mechanism have been developed. Thermogravimetric and differential thermal analysis reveal an exothermic process that first leads to a weight increase, followed by precipitous weight loss above 240°C due to formation of volatile oxidation products. Isothermal weight gain studies between 25 and 142°C show first-order kinetics below 90°C with a rate constant of 3.10-7 s-1 at 25°C and an apparent activation energy of 16 kcal/mol. A weight gain of more than 40% has been observed at 25°C after 2000 h of exposure to air. A change in first-order kinetics occurs at temperatures above 90°C. Identification of solid oxidation products with photoacoustic infrared spectroscopy reveals that oxygen intercalates into the polymer structure in large concentrations, similar to other electron acceptors. However, oxidative attack on the polymer backbone occurs simultaneously. At elevated temperatures or for long-term oxygen exposure, the concentration of dopant oxygen decreases, probably by intramolecular regrouping of hydrogen atoms, resulting in the formation of hydroxyl groups and enhanced polymer degradation. This mechanism is consistent with the finding of others that the conductivity of polyacetylene upon oxygen exposure increases initially before decreasing significantly with continued exposure, especially at elevated temperatures.
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    Reactive oligomers. II. Polymerization of glycol bis(allyl phthalate)s and glycol bis(allyl succinate)s (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3493-3502 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Seven glycol bis(allyl phthalate)s (GBAP) and four glycol bis(allyl succinate)s (GBASu) as reactive oligomers were prepared and their polymerization behaviors were investigated in detail in terms of cyclopolymerization and gelation as compared with diallyl dicarboxylates. Thus, the rates of polymerization of GBAPs were reduced compared to diallyl phthalate, being attributed to the steric effect on the intermolecular propagation of the uncyclized radical, whereas those of GBASus were enhanced as a consequence of intermolecular association by dipole-dipole interaction in polar GBASu monomers. Cyclization was enhanced in the following order: diallyl aliphatic dicarboxylates series 〈 GBASu series 〈 GBAP series. Gelation was discussed according to Gordon's theory; the actual gel-point conversions increased with an increase in the molecular weight of monomers, although the discrepancy between actual and theoretical gel-point conversion inversely tended to be decreased. The decreased delay in gelation with an increase of the molecular weight of monomers is ascribed to the reduction of excluded volume effects on crosslinking.
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    Head-to-head vinyl polymers. XI. Preparation and characterization of poly(methyl acrylate) and poly(methyl methacrylate) consisting of head-to-head and head-to-tail units through cyclopolymerization of acrylic and methacrylic anhydrides (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3503-3515 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acrylic anhydride (AAn) and methacrylic anhydride (MAAn) were polymerized with radical initiator in polar solvents at high temperatures. The polymers obtained were found to consist of five-and six-membered ring structures by comparing IR spectra of the polymers with those of model compounds, succinic anhydride, and glutaric anhydride. Hydrolysis and methylation of the polymers gave new polymers composed of head-to-head (HH) and head-to-tail (HT) methyl acrylate (MA) or methyl methacrylate (MMA) units. The content of HH unit of these HH/HT polymers was determined by 1H-NMR and 13C-NMR spectra. The softening, glass transition, and thermal degradation temperatures of the poly(MA) with HH and HT units were found to somewhat increase with increasing of the content of the HH units. On the other hand, the glass transition and thermal degradation temperatures of the poly(MMA) with HH and HT units increased similarly, but the softening temperature decreased as the content of the HH units increased.
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    Charge transfer polymerization of 2-vinyl pyridine initiated by n-butyl amine and carbon tetrachloride (1983)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 3517-3524 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Vinyl pyridine (2-VP) can be initiated by a charge-transfer complex formed by the interaction of aliphatic amines such as n-butylamine (nBA) and carbon tetrachloride (CCl4) in a solvent like NN-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). This article describes the polymerization of 2-VP by n-butylamine (nBA) in the presence of carbon tetrachloride in DMSO at 60°C. The rate of polymerization Rp increases rapidly with carbon tetrachloride (CCl4) up to a concentration of 3.93 mol/L, but for a higher concentration it is almost independent of the carbon tetrachloride concentration; Rp is proportional to [nBA]0.5 and [2-VP]1.5 when [CCl4]〉[nBA]. The average rate constant k is 1.03 × 10-5 L/mol s. When [CCl4] 〈 [nBA] the rate constant in terms of [2-VP] was 1.06 × 10-5 s-1 at 60°C and the overall rate constant was 1.035 × 10-5 L/mol s at 60°C.
    Additional Material: 7 Ill.
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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.
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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 
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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: 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.
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    System development for aqueous gel permeation chromatography (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 287-293 
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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: To devise an improved gel permeation chromatography system for the analysis of macromolecules, with a strongly alkaline solution as eluent, three Fractogel TSK gels were investigated. Because primary standards are usually unavailable, calibration was achieved by using Benoit's universal procedure and polystyrene sulfonates, polyethylene glycols, and dextrans as secondary calibrants. Continuous monitoring of intrinsic viscosity resulted from coupling a viscodetector with a classical differential refractometer. It was found that column efficiency and fractionation range could be extended well beyond those of previously studied systems on a reasonably short period of analysis.
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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 
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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 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.
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    Structure and immunological properties of polyacrolein formed by means of ionizing radiation and base catalysis (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 609-621 
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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 the formation of polyacrolein microspheres by ionizing radiation (polymer I) were investigated. Their structure and reactivity were compared with polyacrolein microspheres prepared by base catalysis (polymer II). The study of Fourier infrared (IR) spectra of polymers I and II showed structural differences. The reaction of polyacrolein spheres with m-aminophenol indicated the presence of conjugated groups. The reaction of antibodies with polyacrolein spheres was investigated as a function of pH and the number of reactive aldehyde groups was determined by nitrogen analysis of polyacrolein-hydroxylamine adducts. Intensely fluorescent polyacrolein microspheres obtained by Co-γ-irradiation in sizes of 100 Å-4 μm have already found applications as immunoreagents for cell labeling and separation.
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    Cationic polymerization of β-pinene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 673-677 
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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: β-Pinene was polymerized with cationic initiators in reactions that were carried out to study the solvent, temperature, initiator, and monomer-to-solvent ratio. Polymers obtained under different conditions were characterized by intrinsic viscosity, softening point, and gel permeation chromatography.
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    Microstructures of polybutadienes prepared by anionic polymerization in polar solvents. Ion-pair and solvent effectsNational Research Council of Canada Number 22899. (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 669-672 
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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 microstructure of polybutadiene produced by anionic initiation in diethyl ether and tetrahydrofuran with counterions Li+, Na+ and K+ was determined by 1H- and 13C-NMR. Ionization suppressing salts were added in tetrahydrofuran to ensure that only the ion-pair reaction was studied. Results are compared with older published data. In general, the 1,4 content of the polymer increases with increasing counterion size but varies somewhat with solvent with a given counterion. The cis component of the 1,4 structures changes with temperature and counterion. It is suggested that this change reflects the proportion of cis and trans centers that carry the reaction.
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    Reversible protection of oligomeric ethylene glycols by bis (2,4-dinitrophenylation) and basic ethanolysisPresented at Israel Chemical Society, 46th Annual Meeting, June 1979, Jerusalem. (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 657-667 
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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: Bis-(2,4-dinitrophenyl)glycols are stable in the presence of triethylamine but undergo ethanolysis in the presence of hydroxide ions. The quantitative removal of the DNP blocking group allows an integrated scheme to pure glycols from commercially available polyethylene glycol mixturesMixtures of ethylene glycol oligomers are obtained by anionic polymerization of ethylene oxide. See, for example, G. O. Curme and F. Johnston, Glycols, Reinhold, New York, 1953. They are commercially available (as PEG-200, PEG-400, etc., to indicate the average molecular weight of the major components). by bis-dinitrophenylation, chromatographic separation, and end-group removal, using high performance liquid chromatography (HPLC) of the bis-(2,4-dinitrophenyl)glycols for purity monitoring. A facile synthetic method for the production of penta-to dodecaglycols in a mixed, aqueous, dioxane solvent system, with fair yields, is also described. The bis-(2,4-dintrophenyl) protection of glycols is a reversible reaction that can be used as (1) a preparative method for pure glycols from readily available commercial polyethylene glycol mixtures; (2) a highly sensitive and accurate analytical methodA. Warshawsky, A. Tishbee, and N. Shoef, J. Liq. Chromatogr., submitted for publication. coupled with HPLC.
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    Synthesis and characterization of sulfonated poly(acrylene ether sulfones)This paper is dedicated to Professor V. T. Stannett on the occasion of his 65th birthday. (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 721-737 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ionic groups incorporated into a polymer have a decided effect on its physical properties. A number of ionomers and polyelectrolytes have been widely applied. In particular, sulfonated bisphenol-A polysulfone (SPSF) has been used as a composite or single-component membrane for the desalination of water. In this article, the synthesis and physical characteristics of sulfonated polysulfone are addressed. A detailed synthesis route is provided and methods that yield determinable levels of sulfonation are described. These ion-containing polymers retain an excessive amount of residual salts, which, of course, are impurities to the system. Therefore, before any analyses were made the polymers were subjected to a thorough soxhlet extraction process with boiling water, which appeared to be quite effective. The degree of sulfonation was assessed by several methods such as 1H NMR and FT-IR. A new 1H NMR method was derived because the method cited in the literature proved to be too inconsistent for our work. The new 1H NMR method used a quaternary ammonium counterion [N(CH3)4]. These methyl protons are easily measured and may be ratioed against the isopropylidene protons in the polymer backbone that act as an internal standard. Characterization of the physical properties of SPSF consisted of water uptake, differential scanning calorimetry (DSC), thermomechanical analysis (TMA), and solubility studies. Its physical appearance and mechanical behavior were improved by the solution procedure. Also addressed were the effects of different counterions (Na+ & Mg++) with SPSFs of low levels of sulfonation. The variation in physical properties between the divalent and monovalent counterions is dramatic, especially when observed by TMA in the rubber plateau above the apparent glass temperature.
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    Diffusion-controlled reaction. VI. Radiation graft polymerization of styrene to polyethylene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 769-779 
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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 radiation graft polymerization of styrene to polyethylene was studied under diffusion-controlled conditions of radiation intensity I, monomer concentration M1, and polymer sample thickness L. The results of the present study together with previous work under diffusion-free conditions verify our theoretical model for the diffusion-controlled reaction. The grafting rate is inverse first order in L for diffusion-controlled reaction and independent of L for diffusion-free reaction. The order of dependence of grafting rate on radiation intensity for diffusion-controlled reaction is one-half that for diffusion-free reaction. Diffusion control leads to a decrease in the order of dependence of grafting rate on monomer concentration. The decrease is greater than theoretically predicted; possible reasons for this effect are described.
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    Polyhydroxymethylfuroate [poly(2,5-furandiylcarbonyloxymethylene)] (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 863-864 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220336
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    Synthesis and characterization of poly(amide-amine) polymersNCL Communication No. 3282. (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 985-994 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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    Interpenetrating polymer networks from polyurethanes and methacrylate polymers. II. Interpenetrating polymer networks with opposite charge groups (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1035-1042 
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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: Interpenetrating polymer networks (IPNs) with opposite charge groups (tertiary amine and carboxyl groups) made from polyurethanes and methacrylate polymers have been synthesized and their properties and morphology, studied. With increasing carboxyl group concentration the mechanical properties and compatibility between the component networks were significantly improved, possibly because of the negative (or zero) free energy produced by the interaction contribution between the tertiary amine groups in the polyurethanes and the carboxyl groups in the methacrylate polymers determined by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The improved molecular mixing in these IPNs was thought to be due to the influence of the opposite charge groups in these systems.
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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 
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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 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.
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    Synthesis and investigation of polymers based on the nitriles of polycarboxylic acids and diamines (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1043-1053 
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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 influence of the reaction medium on the polycondensation of the tetranitriles of tetracarboxylic acids and diamines has been investigated. The reaction in phenol and cresols yields polymers with macroheterocycles in the chain - polyhexasocyclanes. If phenols with electron-accepting substituents are used as reaction medium, nonmacrocyclic polymers with side aroxyl groups in the chain, polyisoindoxazenes - are formed. The properties of these polymers were studied. Macroheterocyclic compounds formed by condensation of phthalodinitrile with diamines can be used as one of the initial substances in polyhexasocyclane synthesis. Polyamidohexasocyclanes were prepared by polycondensation of macroheterocycles with dicarboxylic acid dichlorides. Some regularities of their formation and their properties were investigated.
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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.
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    Synthesis and characterization of polymers and copolymers of vinylruthenocene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1077-1084 
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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 vinylruthenocene and its copolymers with methyl acrylate, styrene, and n-vinylpyrrolidinone have been prepared by free-radical polymerization. No evidence for the electron transfer termination mechanism postulated for polymerization of vinylferrocene was observed. Yields of soluble polymers were 40-90% with Mw (4-25) × 103 and Mw/Mn = 3.0-13.2. TGA analysis showed little weight loss up to 300°C but rapid decomposition above 300°C. Polyvinylruthenocene is a highly brittle material with Tg above 250°C. Torsional braid analysis of the copolymer samples showed Tg in the range 90-130°C which in some samples increased upon cooling and reheating. Several samples showed weak thermal transitions occurring prior to or following Tg. The rise in Tg upon cooling and reheating is indicative of possible decomposition, crosslinking, or realignment of the polymer chains.
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    Chemistry of alkenyl azlactones. I. Radiation-sensitive materials derived from azlactone-containing copolymers (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1179-1186 
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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: 2-Vinyl-4,4-disubstituted azlactones were shown to be effective comonomers in free radical addition polymerizations for purposes of subsequently preparing radiation-sensitive materials by attaching an unsaturated nucleophile. The azlactone-functional copolymers could be reacted with amine-, thiol-, and hydroxy-functional nucleophiles over the course of a few hours in solution at room temperature to effect covalent attachment of the nucleophile. The electron beam- and UV-sensitive materials were shown to be useful as photoresist and embossable video disk recording media.
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    Synthesis and conformation of asymmetric rigid polyamides (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1153-1177 
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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: Asymmetric polyamides from the reaction of either optically active trans-1,2-cyclopropanedicarboxylic acid (C3) or trans-1,2-cyclohexanedicarboxylic acid (C6) with 2,7-diazaspiro[4,4]nonane(DSN) were synthesized. The possible conformations of these polymers and their model compounds in 2,2,2-trifluoroethanol (TFE), water, methanesulfonic acid (MSA), and sulfuric acid were examined by circular dichroism (CD), NMR, viscosity, and dipole moment measurements. The racemic polyamides (±)C3·(±)DSN and (±)C6·(±)DSN exist in extended forms. No intrinsic viscosity changes were observed for these two polymers in TFE and MSA. Certain viscosity and spectral changes have been observed for the optically active polyamides, although no specific ordered conformations can be assigned. The optically active diacid units incorporated into the polymer give a conformation unique from the totally extended chain. CD studies seem to evidence some conformational differences among the polyamide derived from (+)C6 diacid and the optically active DSN. By changing the solvent from TFE to MSA a blue shift of the trough was observed for (+)C6·(±)DSN, a red shift for (+)C6·(-)DSN, and an inversion of the CD spectrum for (+)C6·(+)DSN polyamides. The results of the work with (+)C6·(-)DSN in dilute acid solution suggest that the rotation around the C-N bond is a relatively low-energy process. The spectral and intrinsic viscosity data are consistent with this suggestion. No drastic spectral changes have been observed for the C3·DSN polyamides by changing the solvent from TFE to MSA. The amide group in the C3·DSN polyamide and the corresponding model compound prefer a similar conformation with the carbonyl group bisecting the cyclopropane ring. The C3·DSN polyamide seems to exist in an extended form.
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    Phase-transfer reactions catalyzed by phosphonium salts bound to macroporous polystyrene supports (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1243-1250 
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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 rate of reaction of alkyl halides with aqueous sodium acetate or cyanide catalyzed by phosphonium salts supported on insoluble polystyrene resins, and rates of ion-exchange of the chloride ion in the catalysts against the acetate ion, were studied as a function of catalyst particle size, the percentage of ring substitution, the morphology of polymer support, and distance between active site and polymer backbone. Rates of 1-bromooctane or benzyl chloride with macroporous, 7-25% ring-substituted catalysts increased with increasing ring substitution. Rates with macroporous catalysts increased as a heptamethylene spacer was introduced between the active site and the polymer backbone. Rates of ion-exchange with macroporous catalysts were facilitated with increasing ring substitution or by the introduction of the spacer chain. A relation between the catalytic activity of macroporous or microporous catalysts and ion-exchange rates under triphase conditions was discussed.
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    Living reversible anonic polymerization of N,N-diethylamine-1,3,2-dioxaphosphorinan (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1251-1258 
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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: Polymerization of the cyclic amide of PIII is described for the first time. The N,N-diethylamine-1,3,2-dioxaphosphorinan was shown to give living reversible polymerization with anionic initiators. Lithium and sodium derivatives were found to be inactive. 1H-, 13C-, and 31P-NMR indicated that the polymer strictly reflects the monomer structure and is formed without any isomerization, the polymer chain being $\rlap{--} ({\rm OP}\left( {{\rm NR}_{\rm 2} } \right){\rm O(CH}_{\rm 2} \rlap{--} )_3 )_n $. Initiation involves attack of the anion on the P atom. From the dependence of the equilibrium monomer concentration on temeprature ΔH1s = 1.5 ± 0.2 kcal·mol-1 and ΔS1s = 4.6 ± 0.6 cal·mol-1·°K-1.
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    Photochromism of 4-acryloxyazobenzene/(-)-menthyl acrylate copolymers (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1267-1280 
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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: Copolymers of trans-4-acryloxyazobenzene (AAB) with (-)-menthyl acrylate (MtA) have been prepared by free radical initiation; comonomer reactivity ratios have been found to be rAAB = 0.89 and rMtA = 0.53. Dependence of chiroptical properties on copolymer composition has been investigated and contribution to circular dichroism by azobenzene chromophores of isolated and sequence AAB units, as well as the influence of the trans to cis photoisomerization, have been determined. Kinetics of photoinduced trans → cis and thermally induced cis → trans isomerization of azobenzene side chains have also been examined and the kinetic parameters evaluated with relation to copolymer structure. The results have been discussed in terms of light-induced secondary structure reversible modifications.
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    Preparation and properties of high transition temperature aromatic polyphosphonates by phase-transfer-catalyzed polycondensation of phenylphosphonic dichloride with bisphenols (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1259-1265 
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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: Aromatic polyphosphonates of high molecular weights were prepared from phenylphosphonic dichloride and bisphenols having rigid ring structures by the two-phase polycondensation in organic solvent-aqueous alkaline solution system with phase-transfer catalyst at 0°C or below. The effects of reaction solvent and catalyst on the inherent viscosities of the polymers formed are studied. The glass transition temperatures of the polyphosphonates with biphenyl, phenylindane, and diphenylfluorene units are 120, 124, and 188°C, respectively. These polymers are self-extinguishing and are readily soluble in solvents such as N,N-dimethylacetamide, pyridine, tetrahydrofuran, and chloroform. They began to lose weight above 300°C in air. Copolyphosphonates from combinations of bisphenols and phenylphosphonic dichloride are also prepared and characterized.
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    Syntheses and electrical conductivity of polyamides containing tetrathiafulvalene moieties in the main chain (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1299-1307 
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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: Novel polyamides that contain tetrathiafulvalene (TTF) moieties were synthesized by direct polycondensation of Δ2,2′ -bi-1,3-dithiole-4,4′(5′)-dicarboxylic acid with aromatic diamines in the presence of triphenylphosphine, hexachloroethane, and pyridine. Complexes of these polyamides with bromine were TTF cation radical () salts which resulted from the charge transfer of TTF moieties to bromine. The electrical conductivity of undoped polyamides increased with a decrease in diamine length. By doping the bromine the conductivity of the polyamides was enhanced by 3-5 orders of magnitude and reached 10-5-;10-9S cm-1. Maximum conductivity was observed at the doping ratio of [Br]/[repeat unit] 〈 1. The electrical conduction in the bromine complexes may be attributed to the hopping of odd electrons of between TTF moieties.
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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 
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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 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.
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    Preparation and properties of aromatic polyesters and copolyesters containing phenylindane unit (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1319-1325 
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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: Aromatic polysters and copolyesters of high molecular weights with phenylindane units were prepared from combinations of 3-(4-hydroxyphenyl)-1,1,3-trimethyl-5-indanol and bisphenol A with isophthaloyl and terephthaloyl chloride by two-phase polycondensation in a nitrobenzene-water system with various phase-transfer catalysts. The phenylindane-containing polyesters and copolyesters were amorphous and readily soluble in a wide range of solvents that included chloroform, m-cresol, tetrahydrofuran, and dimethylformamide. The glass transition temperatures of the phenylindane-derived polyisophthalate and polyterephthalate were 235 and 253°C, respectively, which were higher than those of the corresponding bisphenol A analogs by some 50°C. These polymers began to lose weight around 400°C in air and nitrogen atmospheres.
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    Graft polymerization of acrylic monomers onto starch fractions. III. Effect of carbohydrate structurePresented in part at the Macro '83, 29 Symposium of IUPAC. (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1327-1333 
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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: Grafted PMMA was isolated by the acid hydrolysis method. Weight-average and number-average molecular weights were determined by gel permeation chromatography. The number-average molecular weight of the grafted chains was about 475,000 for amylopectin and 403,000 for amylose. The number of grafted chains (mmol) ranged from 2.4 × 10-3 to 4.6 × 10-3 for amylopectin graft copolymers and from 2.9 × 10-3 to 6.8 × 10-3 for those of amylose. These results were related to others obtained from ceric ion consumption studies. The values suggest that amylopectin, because of its complex structure, favors a higher consumption of ceric ion in homopolymerization reactions and inhibits the initiation reactions of the copolymerization.
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    Functionalization of an amorphous ethylene-propylene copolymer by free radical initiated grafting of unsaturated molecules (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1335-1347 
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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: Functionalization of an amorphous ethylene-propylene copolymer, EPM, has been performed by means of homogeneous grafting reactions of unsaturated molecules such as dibutylmaleate, diethylfumarate, itaconic anhydride, and maleic anhydride, initiated by free radicals. Dicumylperoxide and dibenzoylperoxide have been used as a free radical source and their efficiency has been compared. A different reactivity of the unsaturated molecules has been evidenced. The influence of the nature of the solvent on the functionalization degree has been investigated, revealing a noticeable effect of the solvent either on the amounts of grafted molecules or on the secondary reactions which lead to partial degradation of the functionalized EPM chains.
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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 
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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: 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.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220618
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    The preparation and characterization of homogeneous copolymers of ethylene and 1-alkenes (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1383-1392 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Homogeneous copolymers of ethylene and 1-alkenes have been prepared using an ethyl aluminum sesquichloride-vanadium oxychloride catalyst system. Branches were varied from CH3 to C16H33 by appropriate choice of 1-alkene. Size exclusion studies of copolymers of ethylene-d4 and 1-alkenes show that the comonomer content of a given sample is essentially constant over the whole molecular weight range. A random distribution of branches is inferred from the simplicity of the 13C-NMR spectra and from the melting behaviour of the copolymers. Comonomer contents varying from 1 mol% to 15 mol% were readily determined by 13C-NMR spectroscopy. The copolymers can be used to study the separate effects of branch length, branch frequency, and molecular weight on physical properties including melting point and crystallinity.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220619
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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.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220622
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  • 186
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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.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220624
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  • 187
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    Block copolymers derived from azobiscyanopentanoic acid. IV. Synthesis of a polyamide-polystyrene block copolymer (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1611-1621 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyamides 6.10 and 6.6 (PA* 6.10 and 6.6) containing small amounts of —N=N— units in the main chains were prepared by interfacial polycondensation between hexamethylenediamine and sebacoyl chloride or adipoyl chloride with addition of azobiscyanopentanoyl chloride. Polyamide-polystyrene block copolymers (PA-b-PSt) were then prepared by decomposition of the —N=N— units of PA*, initiating radical polymerization of styrene in m-cresol. The average PA block length of PA-b-PSt thus formed was longer than that expected from the initially present PA segments between the —N=N— units. This is probably due to recombination of PA radicals whose initiation efficiency is as low as 15%. The PSt blocks also had higher molecular weight (7000-79,000) in comparison with homopolystyrene produced from monomeric azobiscyanopentanoic acid used as an initiator due to higher viscosity of polymerization system. Variation of intrinsic viscosity and turbidimetric titration behavior along with the change in composition were also discussed.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220709
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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 
    Details
    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.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220715
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  • 189
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    Temperature dependence of the laser-initiated polymerization of a thiol-ene system (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1865-1873 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The laser-initiated polymerization of a thiol-ene photopolymerizable system was studied. The laser was operated in single- and multiple-pulse modes to generate exotherms, which were measured in a modified differential scanning calorimeter. Arrhenius plots of the polymerization, obtained by measuring polymerization exotherms at various temperatures, showed positive and negative portions. Pseudoactivation energies for the thiol-ene polymerization increased rapidly at low conversions (〈50%) of the thiol and ene chromophores. The results were comparable to those obtained from photopolymerization of multifunctional acrylate monomers.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220808
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    Solution behavior of ampholytic styrene ionomers (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2005-2016 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this article are described the solution properties of ampholytic ionomers obtained by the radical copolymerization of styrene with the ion-pair comonomer 3-methacrylamidopropyltrimethylammonium, 2-acrylamido-2-methylpropanesulfonate. The solution properties were studied in mixed solvents, with a good solvent for the polystyrene backbone and another for the ionic moieties, and in the individual good solvent of benzyl alcohol. The data obtained strongly support extensive intermolecular ionic interactions in solution.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220906
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    Differential scanning calorimetry studies of irradiated polyethylene: II. The effect of oxygen (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2033-2045 
    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 absorbed doses of ionizing radiation up to 2MGy in the presence of air on the melting behavior of high- and low-density polyethylene was analyzed from data obtained by differential scanning calorimetry. Thermal measurements were made during the first melting after irradiation. The first melting temperature of polyethylene irradiated in air decreased with increasing absorbed dose. Above approximately 0.6 MGy bimodal endotherms were observed for high-density polyethylene. The heat of fusion remained unchanged after irradiation in air for absorbed doses of less than 2 MGy. Bimodal endotherms were not obtained for low density polyethylene samples irradiated in air. The changes in melting temperature and the appearance of bimodal endotherms are related to the radiation chemistry of polyethylene in the presence of oxygen.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170220908
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    Conformation of poly(S-(2-N-carbazolylethyl)-L-cysteine) in the solid state (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2047-2059 
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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 β-forming characteristics of poly(S-(2-N-carbazolylethyl)-L-cysteine), (CELC)n, were examined by infrared (IR) spectroscopy. The film of (CELC)39 cast from tetrahydrofuran (THF) showed the typical spectrum of the antiparallel β-form with the amide I band at 1630 cm-1, whereas that of (CELC)200 from dimethylformamide (DMF) or pyridine exhibited the amide I band at 1640 cm-1 which shifted to 1630 cm-1 on heating at 100°C for 5 min. As a result of the examination of the spectral variation due to the degree of polymerization, casting solvents, casting temperatures, and heat treatment, together with the evaluation of interaction constants for intermolecular hydrogen bonds, the band at 1640 cm-1 was attributed to the antiparallel-chain pleated sheet (designated as β′-form) with weaker hydrogen bond strength than that of the usual antiparallel β-form. The β′-β-transformation is discussed in terms of the rigidity of the side-chain region.
    Additional Material: 8 Ill.
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    Differential scanning calorimetry studies of irradiated polyethylene: I. Melting temperatures and fusion endotherms (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2017-2032 
    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 ionizing radiation on the melting behavior of high-density and low-density polyethylene was examined with data obtained by differential scanning calorimetry. Melting temperatures and fusion endotherms were obtained after absorbed doses of gamma radiation up to 3 MGy. The changes in melting temperatures and heat of fusion for the first and second meltings are related to the radiation chemistry of polyethylene. The changes in the first melting temperature are caused by radiation-induced links that decrease the melt entropy and increase the flod surface free-energy-per-unit area of chain-folded polyethylene crystals. These effects are dependent on the lamellar thickness distribution and on the types of links formed (intramolecular or intermolecular). The changes in melting temperature and heat of fusion obtained in the second melting are related to the inhibition of crystallization caused by the presence of radiation-induced links.
    Additional Material: 8 Ill.
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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 
    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 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.
    Additional Material: 5 Ill.
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    Synthesis, characterization, and properties of novel aromatic bispropenyl ethers (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2105-2121 
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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: Aromatic bispropenyl ethers are a new class of highly reactive thermosetting monomers that have been prepared and characterized. Two synthetic routes to their preparation have been developed. The first of these involves the base-catalyzed isomerization of bisallyl ether precursors that gives predominantly the Z bispropenyl ether isomers. The second method employs tris(triphenylphosphine)ruthenium(II) dichloride as an isomerization catalyst and produces predominantly the E isomers. Using these methods, a number of bispropenyl ether monomers containing different aromatic groups have been synthesized. The cationic polymerization of these novel monomers to give crosslinked network polymers using diaryliodonium salts as photo and thermal initiators has been studied.
    Additional Material: 11 Ill.
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    Hydrogen as a chain terminator in continuous gas phase polymerization of propylene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2255-2263 
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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 effects of hydrogen on both degree and rate of polymerization have been determined for continuous, gas phase polymerization of propylene at industrial reactor conditions. The effects of molecular weight using three modifications of TiCl3-DEAC catalyst are correlated by Natta's equation, using number average molecular weights determined from polymer melt flow rate. The coefficients of Natta's equation, when correlated against temperature in Arhenius plots, imply that the most active catalyst is diffusion controlled because the activation energy is abnormally low. Hydrogen increases overall polymerization rate. Rate is correlated by modification to Natta's equation that accounts for hypothesized increase in active sites on catalyst surface due to adsorbed molecular hydrogen.
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    Polymerization of methyl methacrylate up to high degrees of conversion: Experimental investigation of the diffusion-controlled polymerization (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2243-2253 
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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 kinetic model given by Marten and Hamielec that describes the bulk polymerization of methyl methacrylate (MMA) and accounts for diffusion-controlled termination and propagation was modified to include termination by combination and reaction diffusion and was then tested using isothermal conversion/time and molecular weight data obtained dilatometrically at various temperatures and with three different initiators. For each series of measurements two adjustable parameters were fitted to the conversion/time data. Excellent fits were obtained and the adjustable parameters were found to be the same for all concentration levels of the three initiators and to vary in a simple manner with temperature. The predicted molecular weight averages and molecular weight distributions were in satisfactory agreement with those found experimentally considering the difficulty of measuring high molecular weight PMMA by GPC. This model thus satisfies the specifications for a polymer reactor model that can be used to optimize commercial production systems.
    Additional Material: 4 Ill.
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    Polymerization of 1-bromo-2-phenylacetylene by Mo catalystsPart 16 of Polymerization of Phenylacetylenes. For Part 15 see ref. 1. (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2275-2279 
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    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.1984.170220927
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    An ESCA study of the inductively coupled RF plasma polymerisation of 2,4,6-trifluoro-1,3,5-triazine (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2661-2666 
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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: ESCA has been used to investigate the composition and structural features of plasma-polymerized 2,4,6-trifluoro-1,3,5-triazine. Polymer formation was studied as a function of power and post-polymerisation treatment. All the polymer films revealed an intense peak at a binding energy of ∼290.2 eV probably arising from groups. A high sensitivity towards hydrolysis was observed resulting in substantial loss of fluorine and increase in oxygen content of the plasma polymers.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1984.170221030
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    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.
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    URL: http://dx.doi.org/10.1002/pol.1984.170221032
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