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  • 1970-1974  (3,036)
  • Physics  (2,547)
  • Engineering General  (489)
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 105-120 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radiation-induced emulsion polymerization of ethylene with ammonium perfluoro-octanoate as an emulsifier was studied in order to elucidate the effect of the number of polymer particles. Owing to the stable structure of the emulsifier from a radical attack, no C—F bond was detected in the polyethylene as expected. The polyethylene produced was mostly gel containing a small amount of low molecular weight polyethylene. This may be attributable to chain transfer to the polyethylene. The effects of dose rate and of concentration of the emulsifier were determined without considering the chain-transfer reaction to the emulsifier. By considering the escape of the radical which is produced by chain transfer to the monomer from the polymer particle to the aqueous phase at the steady state, the following equation is derived: \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{R_p }}{I} = \frac{{K_i K_p ^2 [{\rm N}_{\rm T} ]}}{{2K_0 \alpha R_p }} - \frac{{K_i K_p }}{{K_{0\alpha } }} $$\end{document} The experimental results could be explained by this equation, and the apparent rate constants were obtained.
    Additional Material: 22 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 183-189 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Anionic polymerization of phenyl vinyl ketone (PVK) was carried out in toluene at 0°C by use of an initiator, ethylzinc 1,3-diphenyl-1-pentene-1-olate (I), which possesses the same structure as the growing chain end of PVK in the diethylzinc (ZnEt2)-initiated polymerization. A unimodal molecular weight distribution was found in the obtained polymer. The polymerization system exhibited a “living characteristic” with the initiator efficiency being 1.0.
    Additional Material: 2 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 167-181 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of a Mannich base type-polyamine polymer with iodine (I2) was studied kinetically and thermodynamically in order to clarify the polymer effects in the formation of triiodide ions (I3-). N,N-Dimethyl-p-(4-methylpiperazinomethyl) aniline and 1,4-dimethylpiperazine were used as low molecular weight donor model compounds. Triiodide ions are produced from the polyamine-I2 system immediately after mixing the two-component solutions, while in the systems with I2 and N,N-dimethyl-p-(4-methyl-piperazinomethyl)aniline and 1,4-dimethylpiperazine they are obtained only when relatively high concentrations of both donor and acceptor solutions were mixed. This is explained by the entropic contributions of the polymer chain such as the stacking effect of donor nitrogen atoms, i.e., the increment of local donor concentration around I2 in the reaction field. The relation between the solution behavior of the reaction systems and the rate of formation of I3- ions also supports this kind of polymer effect. The effects of neighboring groups and dielectric constant on the reaction are also discussed.
    Additional Material: 13 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 201-210 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to examine effect of the carbonyl group in carbon monoxide-vinyl chloride copolymer, poly(CO-VC), photoirradiation with a high-pressure mercury lamp on the copolymer was carried out. Poly(CO-VC) had a rate of dehydrochlorination three times that of PVC, and the reaction involved a decrease in chlorine content. Also there was a marked change in the ultraviolet spectra of the photoirradiated films. However, no pronounced change of molecular weight was observed, but a change in Rf in TLC was observed clearly. These facts confirmed that photoirradiation of poly(CO-VC) produced a structural change by dehydrochlorination without serious decrease of molecular weight. In addition, photodehydrochlorination of the copolymer or PVC film was followed kinetically, and after ozonolysis of the dehydrochlorinated polymers, the number-average molecular weights were measured. From the results of degree of dehydrochlorination and molecular weight, the number average of conjugated double bonds or carbonyl groups was estimated. A mechanism for dehydrochlorination process by photo-irradiation is suggested.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 241-246 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 231-240 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Research was carried out on copolymerization of isoprene with maleic acid monoesters in the presence of free radicals (AIBN). The aim of the study was to observe the effect of the different monoesters obtained with normal alcohols of the aliphatic series: monoethyl maleate, monopropyl maleate, monobutyl maleate, monoheptyl maleate, monolauryl maleate, and monocetyl maleate. On the basis of reactivity ratios determined by the Fineman-Ross method and compared with the Mayo-Lewis method, all the systems studied are typical cases of heterocopolymerization. The parameter r1 is constant for this homologous series with the exception of the low terms. The experimental results agree with the ultimate model equation (with deviation at very high values of [M10]/[M20]), but not with the copolymer composition equation which considers the effect of the penultimate unity (penultimate model). Characterization of the sequential distribution is also presented (considering the effect of the terminal group only), and deviations of the experimental results are also discussed.
    Additional Material: 6 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 255-264 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chlorinated poly(vinyl chloride) (CPVC) is known to have a higher softening temperature than conventional poly(vinyl chloride) (PVC). Its processability characteristics are, however, different; it has been reported that CPVC is more difficult to process. However, only limited information on the processability characteristics is available. This paper describes some studies of the flow behavior of CPVC melts in a capillary rheometer. The true melt viscosity and activation energy were determined between 190° and 210°C for a number of samples, and they appear to be related to the cohesive energy density of the samples. It was observed that melt fracture, i.e., gross distortion of the extrudate, occurs even at low shear rates in samples having a high chlorine content. This has been attributed to the relatively high pressures that have to be used, the pronounced non-Newtonian nature of the melt, and melt elasticity. It is postulated that melt elasticity could result from crosslinking at the site of the double bond which is known to be formed by dehydrochlorination.
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  • 8
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new mechanism has been proposed for the photooxidation of polystyrene as film and in benzene. The initial stage of the photooxidative degradation may involve reactions of singlet oxygen with polystyrene molecules. Singlet oxygen may be formed in the reaction between excited benzene ring in polystyrene molecule and molecular oxygen. The addition of singlet oxygen quenchers such as 1,3-cyclohexadiene or β-carotene reduces the rate of polymer degradation in benzene solution. The mechanisms of the photolysis of polystyrene as film and in benzene solution, in vacuo and in the presence of oxygen, are discussed and interpretations proposed. The pronounced yellowing of polystyrene during the photooxidation process is interpreted as a reaction involving benzene ring-opening photooxidation in polystyrene molecule. These results were obtained by comparing ultraviolet and infrared spectra in experiments of photooxidation of pure liquid benzene and polystyrene film.
    Additional Material: 10 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 307-322 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The detailed design and computer interfacing of a GPC molecular weight detector based on a real time viscometer are described. The working drawings presented will permit one to fabricate and duplicate the viscometer and the complete GPC molecular weight detector system. The uses and advantages of a laboratory automation system in analyzing GPC results are also described.
    Additional Material: 17 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 337-345 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two series of monodisperse polystyrenes have been prepared with a molecular weight range of 3,000 to 300,000. One series was lightly substituted with dimethylbenzylamine groups, the other with 2,6 dinitro-4-benzoyloxyphenol groups. Members of each series were dissolved together in benzene solution in the range of 0.1-30%, and the equilibrium constant for the formation of the ammonium phenolate ion pair measured. Also measured was the corresponding equilibrium constant between comparable small molecular weight analogs, and between these analogs and the substituted polymers. The degree of association found between the models and between the models and the polymers was independent of molecular weight, but deviations were found in the polymer-polymer interaction. Normal equilibrium constants were found at high polymer concentrations indicating that chain interpenetration occurred freely. At low concentrations of polymer, if several links per chain were possible it was found an excess of linkages were formed. If only one link per chain was possible, low degrees of association were found for high molecular weight polymers, but the effect was not as large as a consideration of excluded volumes on a spherical model would predict.
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  • 11
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 357-374 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Benzidinetetrazonium chloride (BTC)-CuCl and BTC-FeCl2 complexes were thermally converted to benzene-soluble poly-4,4′-biphenylene plus small amounts of insoluble material. The soluble fraction was more stable than the insoluble fraction when heated at 300-500°C, although the solubility decreased. BTC in water was converted to an insoluble material by addition of alkali or cuprous ammonia solution. The C/(H + Cl) ratio indicated the existence of three to five side groups for each twenty phenyl groups of the insoluble fraction, while that of the soluble fraction showed few such groups. The number increased to one or more side groups for each phenyl nucleus as both soluble and insoluble fractions were heated to 500°C. A thin film of soluble fraction deposited on a copper plate showed an electrical conductivity in the range 10-2-10-3 ohm-1 cm-1 at 25°C and an energy gap (ΔEg) of 0.2-0.3 eV. However, a compressed specimen of the same soluble fraction showed little conductivity. Solventsoluble samples of substituted poly-4,4,-biphenylene were prepared by the same procedure. These materials cracked on processing, and accurate conductivity measurements could not be made.
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  • 12
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 401-410 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Novel phenylated quinoxaline tetraamines have been prepared and polymerized with 1,4,5,8-naphthalenetetracarboxylic acid in polyphosphoric acid solution. The resulting BBB-type polymers with pendant phenyl groups along the polymer backbone are soluble in m-cresol. The polymers, with inherent viscosities ranging from 0.3 to 0.6 dl/g in sulfuric acid, exhibited thermal stabilities near 500°C under nitrogen and near 400°C in air.
    Additional Material: 1 Tab.
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  • 13
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 627-637 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The emulsion copolymerization of ethylene with hexafluoropropylene was studied by using 60Co γ-radiation as the initiator. The apparent rate of copolymerization is proportional to the 1.6 power of ethylene fugacity. The activation volume was calculated from the pressure dependence of the apparent rate constant of copolymerization and was -30 ml/mole, which is smaller than the value reported by Wada et al. for ethylene polymerization in tert-butyl alcohol. The copolymer produced had a broad composition from ethylene-rich to alternative. As expected, the former was a crystalline, polyethylenelike copolymer, but the latter was an amorphous and rubberlike copolymer. The glass transition temperature of the copolymers increased with an increase in hexafluoropropylene content. The thermal degradation temperature in an atmosphere of nitrogen decreased slightly with introduction of hexafluoropropylene in polyethylene, but the thermal degradation behavior in air was complicated by the introduction of hexafluoropropylene.
    Additional Material: 13 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 709-717 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(ethylene terephthalate) oxidizes on heating at 300°C in an air stream. Various literature has cited crosslinking under such conditions through a butanetriol or a biphenyltricarboxylic acid. In this study gelled polymer was found to contain the latter trifunctional compound, but not the former. In addition, 4,4′-biphenyldicarboxylic acid was found in the degraded gel. There is further indication for the presence of other multifunctional species. All components are consistent with general free-radical arylation mechanisms.
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  • 15
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 679-688 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ferric chloride-photosensitized free-radical initiation was used to generate propagating radicals in polymerization of acrylic acid (AA), methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA), acrylamide (A), and diacetone acrylamide (DAA) in rigid glasses of methanol, ethanol, n-propanol, isopropanol, or acetone at near liquid nitrogen temperatures. When the temperatures of the glasses were increased, primary radicals derived from the solvents reacted with the monomers to yield propagating radicals. Formation and conformational changes of the propagating radicals at different temperatures were studied by electron spin resonance (ESR) spectroscopy. It was concluded that one type of propagating radical was formed in all cases. However, when the temperature of the rigid glass was increased, the structural conformation of the radical that initially allowed the near-equivalent interaction of the α-hydrogen and one of the β-hydrogens with the unpaired electron generated a three-line spectrum.
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  • 16
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 719-727 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New pseudo dibenzoylphthaloyl chlorides, namely, 2,5-dibenzoylterephthaloyl, 4,6-dibenzoylisophthaloyl, and 4,6-di(p-toluyl)isophthaloyl chlorides, were synthesized as monomers. The ring-opening polyaddition reaction of the pseudo dibenzoylphthaloyl chlorides with aliphatic diamines in N-methyl-2-pyrrolidone afforded a new class of polyamides having inherent viscosities of 0.2 ∼ 0.6 in quantitative yield. The solution polymerization was almost completed within 30 min at room temperature. All of the polyamides were soluble in a wide range of solvents including tetrahydrofuran. These polymers began to decompose at around 300°C both in air and under nitrogen as determined by differential thermal analysis (DTA) and thermogravimetric analysis (TGA).
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  • 17
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 729-736 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolymerizations of carbon dioxide and N-phenylethylenimine were carried out with the use of various catalysts and solvents. The infrared spectrum of the polymer produced showed the characteristic absorption peak at 1730-1735 cm-1 based on the urethane linkage.The content of the urethane linkage decreased in the following order: Mn(acac)2 ≈ MnCl24H2O 〉 Al(OBu)3 〉 Ti(OBu)4 〉 ZnCl2 ≫ BF3OEt2 = VCl3 = Mn(acac)3 = FeCl3 = CrCl3 · 6H2O = 0. The manganase (bivalent) catalyst in combination with n-hexane solvent was found to be the best system for the copolymerization, and this system received detailed study. Generally speaking, both the polymer yield and the content of the urethane linkage increased with increasing content of carbon dioxide in the feed as well as with increasing polymerization temperature. From the fractionation of polymer in methanol, it was found that the produced polymer is composed of both homopolymer of N-phenylethylenimine and copolymer of N-phenylethylenimine and carbon dioxide. The content of the urethane linkage of the copolymer thus fractionated was as high as about 80%.
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  • 18
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of polyamides was synthesized by the interfacial polycondensation of 1,2,3,5,6,7-hexahydrobenzo [1,2-c:4,5-c′] dipyrrole with isophthalic, terephthalic, oxydibenzoic, sebacic and adipic acid chlorides. High molecular weight polymers with inherent viscosities ranging from 0.4 to 2.3 dl/g were obtained. Polymerization with isophthaloyl chloride gave the highest molecular weight polymer in this series. These polyamides melt between 350°C and 475°C, depending on structural differences as determined by differential scanning calorimetry (DSC). Rapid weight loss in these polymers was observed in the range of 350-400°C under thermogravimetric analysis in a nitrogen atmosphere. All these polyamides are susceptible to photooxidative degradation. The results were compared with Nomex polymer poly(1,3-phenylene isophthalamide).
    Additional Material: 5 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 793-797 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rectilinear relationship between the integral intensity Bi and fiber density d is used as the basis of a new method for evaluation of the crystallinity index of polyamide fibers (PA-6). To calculate the value of the crystallinity index of the fibers one should have the integral intensity value of the sample and the integral intensities of crystalline and amorphous samples determined under defined instrumental conditions. The method provides a quick and simple means for determining the crystallinity. The method of half-integral intensity may be used only with care when the α-monoclinic polymorphic form dominates in the PA-6 fiber.
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  • 20
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 771-784 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 220-MHz proton magnetic resonance and infrared spectra of stereoregular polypropylenes polymerized with a number of Ziegler-Natta catalysts and isotactic polymers of low molecular weight obtained by thermal degradation of a highly isotactic polypropylene were measured in an attempt to obtain some information on the local regularity. The fraction of thermally degraded polymer soluble in diethyl ether shows stereorandomness (tactie sequence length is quite short), and the portion soluble in n-pentane has stereoblock character. The results so obtained provide strong evidence that racemic dyads of whole polymer consist of two models of racemic dyad isolated and racemic dyads in groups. The polymers prepared with vanadium catalyst systems show stereorandom character and these polymers have \documentclass{article}\pagestyle{empty}\begin{document}$\hbox{-\hskip-1pt-}\hskip-4pt({\rm CH}_2 \rlap{--} )$\end{document} groups formed by two propylene units in a tail-to-tail linkage. Syndiotactic polypropylene has head-to-head and tail-to-tail arrangements of two propylene units and this is the origin of randomness of syndiotacticity.
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  • 21
    Electronic Resource
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 807-816 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The binding of methyl orange, ethyl orange, and propyl orange by polycations involving various apolar pendant groups such as methyl, ethyl, benzyl, or dodecylbenzyl groups has been examined quantitatively by an equilibrium dialysis method at 5, 15, 25, and 35°C. The first binding constants and the thermodynamic parameters in the course of the binding have been calculated. The favorable free energy of the binding is accompanied by an entropy gain and an exothermic enthalpy change. The shorter the alkyl chain of the dyes or the polymers, the more negative is the enthalpy change and hence the smaller is the entropy change. Furthermore, an increase in binding affinity can be created in the polycation upon introduction of hydrophobic groups. In particular, the binding ability of the polycation containing a dodecylbenzyl group for methyl orange is almost 300-fold that of bovine serum albumin. Therefore it is clear that hydrophobic interactions, as well as electrostatic ones, are involved in the binding.
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  • 22
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 817-823 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dimethylaniline (DMA) induces chain transfer in the zinc bromide-complexed donor-acceptor polymerizations of styrene-acrylonitrile to form alternating copolymers. The Mayo plots are linear, but the rates decrease with increase in DMA and degradative chain transfer occurs. Although conventional free-radical transfer agents have negligible effect on the rates or molecular weights, a twentyfold reduction of molecular weight is obtained with DMA. Spectroscopic data indicate the formation of an equimolar complex of DMA and ZnBr2, but the lowering of molecular weight is not attributable to the reduction of the effective ZnBr2, concentration. A possible mechanism involving a competition between [ZnBr2(DMA)2] and [ZnBr2,DMA,AN] is suggested.
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  • 23
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 837-850 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new monomer, 1,1′-bis(dimethylaminodimethylsilyl)ferrocene, was synthesized by two routes and polymerized with three aryl disilanols: dihydroxydiphenylsilane, 1,4-bis(hydroxydimethylsilyl)benzene, and 4,4′-bis(hydroxydimethylsilyl)biphenyl, yielding three different polysiloxanes. Melt polymerizations carried out at 1 torr pressure and 100°C resulted in the highest molecular weight polymers. Intramolecular cyclization competed with intermolecular chain extension in polymerization of the bis(aminosilane) with dihydroxydiphenylsilane, resulting in isolation of a bridged derivative, 1,3,5-trisila-2,4-dioxa-1,1,5,5-tetramethyl-3,3-diphenyl[5]ferrocenophane. Cyclization did not compete significantly during the formation of polymers from this bisaminosilane and the two remaining diols, as evidenced by higher yields and greater molecular weights. These polymers could be cast as tough flexible films, and fibers could be drawn from their melts. TGA and DSC data showed the polymer formed from 1,1′-bis(dimethylaminodimethylsilyl)ferrocene and 1,4-bis(hydroxydimethylsilyl)benzene to be at least as thermally stable as an arylene siloxane polymer which differed from the ferrocenylsiloxane structure only in the replacement of the ferrocene moiety with a p-substituted phenylene linkage. The ferrocene-containing polymers were generally hydrolytically stable under conditions of refluxing THF-H2O(10 : 1) for 1 hr. The polymer-forming reaction was found to follow second-order kinetics, and the specific rate constants for formation of two of the polymers were measured.
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  • 24
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 121-131 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbon dioxide and propyleneimine were allowed to copolymerize without using any catalyst to give a polyurethane with a carbon dioxide content of 10-35 mole-%. The polymer yield, the specific viscosity, and the content of carbon dioxide in the copolymer increased with increasing polymerization temperature. The infrared spectrum of the copolymer showed the characteristic peak assignable to a cyclic urethane(4-methyl-oxazolidone-2) at 1750 cm-1 as well as the peak characteristic of the urethane linkage at 1700 cm-1. The relative intensity ratio of the former absorption to the latter decreased markedly with increasing polymerization temperature. Propyleneimine did not polymerize at all in the absence of carbon dioxide. Polymerizations were also carried out with the use of various solvents. On the basis of these results, a probable reaction scheme of the copolymerization was proposed.
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  • 25
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    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 387-400 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The degradation of the binary polymer blends, poly(vinyl acetate)/poly(vinyl chloride), poly(vinyl acetate)/poly(vinylidene chloride) and poly(vinyl acetate)/polychloroprene has been studied by using thermal volatilization analysis, thermogravimetry, evolved gas analysis for hydrogen chloride and acetic acid, and spectroscopic methods. For the first two systems named, strong interaction occurs in the degrading blend, but the polychloroprene blends showed no indication of interaction. In the PVA/PVC and PVA/PVDC blends, hydrogen chloride from the chlorinated polymer causes substantial acceleration in the deacetylation of PVA. Acetic acid from PVA destabilizes PVC but has little effect in the case of PVDC because of the widely differing degradation temperatures of PVA and PVDC. The presence of hydrogen chloride during the degradation of PVA results in the formation of longer conjugated sequences, and the regression in sequence length at high extents of deacetylation found for PVA degraded alone is not observed.
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  • 26
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 433-444 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis, dilute solution characterization, and thermal analysis of seven polyaryloxyphosphazenes are described. Synthesis is accomplished by the ring-opening polymerization of hexachlorocyclotriphosphazene at 245°C, followed by reaction of polydichlorophosphazene with sodium aryloxide salts in solution at 115°C. Polymers prepared and characterized have the general structure [(ArO)2PN]n, with Ar = C6H5, m- and p-CH3C6H4, m- and p-ClC6H4, p-C2H5C6H4, or p-CH3OC6H4. Elemental and infrared analyses show these polymers are essentially free of reactive chlorine sites. All the polymers displayed high intrinsic viscosities [η] 〉 1 dl/g, in tetrahydrofuran or chloroform. Closer examination of the dilute solution properties of two polyaryloxyphosphazenes revealed high molecular weights (M̄w〉 6 × 105) and broad molecular weight distributions (M̄w/M̄n 〉 4.7). The experimental values for the Z-average radii of gyration, 〈S2〉z1/2, characterized at near theta conditions, are larger than the calculated values for a freely rotating chain, which suggests that these polymers are relatively linear and not highly branched. Thermal analysis revealed second-order glass transitions between -37 and +13°C and first-order endothermic transitions between 43 and 160°C for the different polymers. Although crystalline structure can persist above this first-order transition, this temperature can be regarded as a melting temperature or softening temperature at which films can be molded. Decomposition temperatures, measured in argon and oxygen, ranged from 250°C to 400°C.
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  • 27
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 445-454 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relative availabilities of hydroxyl groups at C(2), C(3), and C(6) on the D-glucopyranosyl units of a particular, highly ordered hydrocellulose II have been studied by means of the reaction of N,N-diethylaziridinium chloride, which introduces 2-(diethyl-amino)ethyl substituents. The hydrocellulose II was formed by hydrolysis of fibrous cotton cellulose II during 40 min reflux in 2.5M hydrochloric acid and is designated EHC-II (exemplar hydrocellulose II) because it represents the most highly ordered (crystalline) particles in a series of hydrocelluloses. The deviation in the distribution of substituents among the 2-O-, 3-O-, and 6-O- positions of the D-glucopyranosyl units in EHC-II from that in a disordered cellulose, in which the three types of hydroxyl groups are equally available, is the basis for estimated availabilities of the three types of hydroxyl groups on the surfaces of elementary fibrils in EHC-II. The experimental values of relative availabilities of O(2)H:O(3)H:O(6)H for EHC-II were 1.0:0.26:0.72 compared to estimated values of 1.0:0.0:.075 for surfaces of elementary fibrils of an idealized, perfectly ordered cellulose II, a model that is based on intensities of x-ray diffraction peaks.
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  • 28
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 483-486 
    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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  • 29
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Surfaces of polystyrene Petri dishes used for cell culture were chemically modified by 5% fuming sulfuric acid. The sulfonation was performed at room temperature for various times. Formation of polar groups takes place essentially on the surface of the polymer. Wettability and ionic character of the modified surfaces were determined by contact angle measurements and surface conductivity measurements, respectively. Radioactive calcium (45Ca) adsorption at these surfaces was investigated by means of radiotracer techniques. The chemical composition (concentration of polar sites produced) of these modified polystyrene surfaces was thus determined. It was found that the wettability of these surfaces is directly related to the concentration of sulfonate groups. The cation-exchange capacity of treated surfaces with inorganic cations (Na+, Mg2+, Ca2+, and Al3+) were determined by the radiotracer technique.
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  • 30
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 521-534 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymers with fluoroalkyl side-groups on three of every four carbon atoms along the polymer main chain were made by treating 1 : 1 copolymers of perfluoroallyl (or methallyl)ethers and maleic anhydride with SF4, and then esterifying the resulting acid fluoride groups with 1H, 1H-pentadecafluorooctanol. Surface wettability of these polymers by polar and non-polar liquids was studied. The critical surface tension (γc) was found by Zisman's method. The dispersion force component of polymer surface energy (γsD) and the polar component of surface energy (γsp) were calculated by the respective methods of Fowkes and Owens. The γc values for several of the highly fluorinated polymers were lower than previously reported for any fluoropolymer but not so low as has been observed for the surface of an oriented perfluoroacid monolayer. In the range 11.4-18.5 dyne/cm, γc approximates γsD for the fluorinated surfaces; however at lower γc values, considerable difference between γc and γsD was noted.
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  • 31
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 535-552 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of pressure, temperature, and additives on the rate of radiation-induced emulsion polymerization of ethylene with FC-143 as emulsifier were studied kinetically. The rate of polymerization was proportional to the 2.5 power of ethylene fugacity, and the apparent rate constant (rate of polymerization/2.5 power of ethylene fugacity) was constant below 78°C. Above this temperature, the rate constant decreased with an apparent activation energy of -8.2 kcal/mole. These facts can be interpreted in connection with the polymer structure and the change of rate of escape of radicals from the polymer structure and the change of rate of escape of radicals from the polymer particle into the aqueous phase. The rate of polymerization decreased on addition of a series of n-aliphatic alcohols due to the chain-transfer reaction and consequent escape of radicals to the aqueous phase. On the other hand, the addition of tert-butyl alcohol increased the rate of polymerization, probably because of its effect in increasing swelling of the polymer particles. Addition of electrolytes increased the rate of polymeriaztion as a result of the increase of the number of polymer particles.
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  • 32
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 565-573 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A useful synthesis of a series of new aromatic sulfone ether diamines, H2NC6H4O\documentclass{article}\pagestyle{empty}\begin{document}$\hbox{---}\hskip-5pt[\ {\rm C}_{\rm 2} {\rm H}_{\rm 4} {\rm SO}_{\rm 2} {\rm C}_{\rm 6} {\rm H}_{\rm 4} \hbox{--} {\rm ORO}\hbox{---}\hskip-5pt ]_n {\rm OC}_{\rm 6} {\rm H}_{\rm 4} {\rm SO}_{\rm 2} {\rm C}_{\rm 6} {\rm H}_{\rm 4} \hbox{---} {\rm OC}_{\rm 6} {\rm H}_{\rm 4} {\rm NH}_{\rm 2} $\end{document}, where n = 0, 1, 2…, which increases the tractability of polyimides, polyamide-imides, and polyamides, was developed. These diamines were prepared by condensing various proportions of sodium p-aminophenate, sodium bisphenates, and dichlorodiphenyl sulfone. The synthetic procedures are now refined to the point where simply coagulating these diamines into water yields high purity polymer-grade sulfone ether diamines. The latter have good tractability; and in some cases, it is possible to extrude and injection-mold these high temperature polymers.
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  • 33
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 603-612 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A nonsolvent preparation of the polyvinylpyrrolidone (PVP) complex provides new insight into the nature of the polymer-iodine interaction. The preparation is obtained by simply mixing PVP with crystalline iodine and is of interest because it provides a system in which no interfering ions are present and only one type of iodine is initially present. The iodine is shown to undergo hydrolysis with moisture in the polymer to give iodide and hypoiodite. The ionic forms of iodine appear to associate with the molecular iodine, resulting in the final stable PVP-iodine complex.
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  • 34
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 613-626 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ring-substituted phenyl propenyl ethers were found to form homopolymers without any rearrangement by metal halides. Phenyl propenyl ethers were less reactive than the corresponding phenyl vinyl ethers in cationic polymerization. In order to study the electronic effect of a substituent on the reactivity, cis-p-Cl,p-CH3, and p-CH3O-phenyl propenyl ethers were copolymerized with phenyl propenyl ether in methylene chloride at -78°C with stannic chloride-trichloroacetic acid, and their 1H- and 13C-NMR spectra were measured. The reaction constant ρ against Hammett σp was -2.1. The cis-phenyl propenyl ethers were slightly more reactive than the corresponding trans isomers. On the other hand, an o-methyl group decreased the reactivity of phenyl propenyl ether. The low reactivity of o-methyl phenyl propenyl ether was attributed to the steric hindrance between the propagating carbocation and the monomer.
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  • 35
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 865-874 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isomeric homopolymers and random copolyesters based on sebacic acid and isomeric hexanediols were synthesized by condensation techniques and characterized by NMR, GPC, intrinsic viscosity, and DSC. Among the homopolymers, only the polyester derived from the linear 1,6-hexanediol was found to be crystalline. Typical melting points were 65-70°C, depending on molecular weight, and a Tg of -62°C was measured on a high molecular weight sample. Other isomeric homopolymers derived from the branched diols 2-methyl-2-ethyl-1,3-propanediol and 2,5-hexanediol were amorphous tacky fluids with glass temperatures of -69 and -66°C, respectively. In the case of the random copolymers, NMR analysis was particularly useful in determining the copolymer composition or the diol isomer ratio. DSC data indicated that all the random copolymers containing the linear 1,6-diol were crystallizable and their melting points depended on copolymer composition. The heat of fusion per repeat unit of poly(hexamethylene sebacate) was found to be 32 cal/g from measurements of the molecular weight dependence of the melting point.
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  • 36
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 455-468 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As difunctional compounds containing an ionic bond in the molecule, divalent metal salts (I) of mono(hydroxyethyl) phthalate were prepared in high purity and high yield. Mg and Ca were selected as divalent metal. Metal-containing polyurethanes containing ionic links in the main chain were synthesized by the polyaddition reaction of I or, I-glycols with diisocyanates. The polyurethane obtained were glassy materials or white powders, depending on the species of diisocyanates and glycols. Close agreement between observed and calculated values of metal content of the polyurethanes were obtained. The viscosities (in dimethyl-formamide) of the polyurethanes decreased markedly with increasing of metal content. Moreover, the decomposition temperatures were lowered by introduction of metals into the polyurethanes. However, the decomposition rates of metal-containing polyurethanes were lower than those of polyurethanes not containing metal.
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  • 37
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 469-481 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of metal-containing polyurethane-ureas containing ionic links in the main chain was synthesized by the polyaddition reaction of hexamethylene diisocyanate with mixtures of metal salts of mono(hydroxyethyl) phthalate and bisureas containing two hydroxyl groups which were obtained from monoethanolamine and diisocyanates. The polyurethane-ureas obtained were generally yellowish powders or solids. Close agreement between observed and calculated values of metal content of the metal-containing polyurethane-ureas was obtained. The viscosities (in dimethylformamide) of polyurethane-ureas decreased markedly with increase of metal content. Moreover, the decomposition temperatures were lowered a little by introducing metals into the polyurethane-ureas. Dimethylformamide, m-cresol, and dimethyl sulfoxide were comparatively good solvents for the metal-containing polyurethane-ureas; however, the polymers were insoluble in all other solvents.
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  • 38
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 499-512 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(2-methylpentene-1 sulfone) underwent random chain scission upon exposure to 1 MeV electron irradiation followed by extensive depropagation from the broken ends of the chain. Above 100°C, both sulfone and aliphatic peaks in the infrared spectrum disappeared at equal rates. An investigation of the kinetics suggested that the chains completely unzip. Below 100°C the initial rate of loss of SO2 was faster than loss of the aliphatic moiety.
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  • 39
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 513-519 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of the copper (II) chelates of norephedrine (I), N-methylnorephedrine (II), N-ethylnorephedrine (III), and N-n-butylnorephedrine (IV) with benzoyl peroxide, cumene hydroperoxide, and 2,2′-diphenyl-1-picrylhydrazyl have been studied. Only the chelates of N-alkyl-substituted norephedrines enter into the reactions with free radicals, while their reactivity increases with the length of the alkyl substituent in the amino group of the ligand. The decomposition of cumene hydroperoxide was catalyzed by all four chelates; the catalytic efficiency increases in the order I〈II〈III 〈 IV.
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  • 40
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 553-559 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-Acryloylbenzotriazole was prepared and polymerized. The resulting poly-1-acryloylbenzotriazole gave pure polyacrylic esters and polyacrylamides by reaction under mild conditions with alcohols and amines.
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  • 41
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 561-564 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Crosslinked polymers of improved properties compared to those of pure polystyrene, are obtained by the thermal or radical copolymerization of styrene with 1,3,5-triisopropenylbenzene. The copolymers are transparent glassy solids, practically insoluble in most organic solvents and easily machineable. They decompose at about 350°C. Copolymers containing 5-30% of 1,3,5-triisopropenylbenzene exhibit the better properties.
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  • 42
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 575-587 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Novel aromatic diamines have been prepared which contain an ordered sequence distribution of thermally stable, flexible, or rigid units. The synthesis of these materials involves a nucleophilic displacement reaction in aprotic solvent with, for example, the alkali metal salt of p-aminophenol, optionally, the salt of a bisphenol and an activated aromatic halide. Such monomers are useful “building blocks” for various polymeric systems but are of special interest in those which can benefit from the high glass transition temperature imparted by polar or rigid moieties, together with improved impact properties conveyed by either groups. Polyimides and polyamide-imides are examples and display high heat distortion temperatures, good solvent resistance, excellent mechanical properties, high thermal and oxidative stability and depending on diamine structure and molecular weight, thermoplastic characteristics. The synthesis and properties of polyamides, polyimides and polyamide-imides based on 4,4′-[sulfonylbis(p-phenyleneoxy)] dianiline are presented in this paper.
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  • 43
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 589-601 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High temperature thermoplastic polyamide-imides were prepared from a new series of aromatic diamines containing the diphenylsulfone unit and alternatively, oxydiphenyl and diphenylisopropylidene units. The polymers were prepared in their completely imidized form by using a facile in situ chemical imidization reaction which offers several advantages over the conventional thermal imidization process. The sulfone-based polyamide-imides exhibited an excellent combination of moldability, thermal stability, mechanical properties and solvent resistance. Analysis of the properties of these polymers in terms of structural variations permits a useful correlation of the effect of various structural units on performance. The polar diphenyl sulfone and amide-imide units increase the glass transition temperature and improve solvent resistance while the oxydiphenyl and diphenylisopropylidene units improve thermoplasticity. Sulfone ether diamine polyamide-imide (VI) offers the best combination of high temperature performance and moldability.
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  • 44
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 639-650 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A polymer, poly(2,5-trimethylene benzimidazole), the first of a new family of nonsymmetrical polymers, was synthesized via an eight-step synthetic route. The polymer, obtained by melt polymerization, is amorphous and in its neutral form behaves as a moderate insulator. It forms 1 : 1 HCl adducts. When cast from formic acid solution, it forms 1 : 1 formic acid adducts. The acid adducts are semiconductors with resistivities in the 106-108 ohm-cm range. Space-charge effects are generated in the adducts as carrier mobility rises.
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  • 45
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 651-662 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,3-Bis(p-phenoxybenzenesulfonyl)benzene and 4,4′-bis(p-phenoxybenzenesulfonyl)-diphenyl ether were polymerized with isophthaloyl and terephthaloyl chloride in Friedel-Crafts type polymerizations. These polymers had 5-cyanoisophthaloyl units in the backbone, obtained by using 5-cyanoisophthaloyl chloride as part of the acid chloride monomer. A number of catalysts were screened to effect the trimerization of the pendant nitrile groups in the polymer to the triazines. Model reactions were carried out for each polymer. Physical and thermal properties of the laminates obtained from these polymers are discussed.
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  • 46
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 663-678 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The recent demonstration of an easy synthesis of diiminosuccinonitrile (DISN) from hydrogen cyanide and cyanogen, the reduction of DISN to diaminomaleonitrile (DAMN), and the use of these compounds to form difunctional heterocycles has made several new polyamide intermediates accessible. The 1- and 2-methyl-1,2,3-triazole-4,5-dicarbonyl chlorides have been polymerized interfacially to form high-melting polyamides of good heat stability. Interfacial polymerization of 1-methylimidazole-4,5-dicarbonyl chloride and trans-2,5-dimethylpiperazine has given a polyamide that is water-soluble. The 2,6- and 2,3-pyrazinedicarbonyl chlorides have been similarly converted to high-melting polyamides. 2,6-Dicyano-3,5-dipiperazinylpyrazine has been prepared from tetracyanopyrazine and piperazine and reacted with toluene diisocyanate to form a strong, stiff polyurea. Polyamides were also made from 2,3-diaminoquinoxaline, 1,4,5,6-tetrahydro-5,6-dioxo-2,3-pyrazinedicarbonitrile, and DAMN.
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  • 47
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 689-705 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The curing of epoxy resins with anhydrides in the presence of dihydroxyl-terminated polyester or polyether modifiers produces block copolymer structures in which one “block” is the crosslinked epoxy/anhydride network and the other block is the linear modifier segment. The morphology of the cured system is dependent upon modifier molecular weight. The critical molecular weight of polycaprolactone and poly(propylene oxide) is 3000-5000. Below this level, single morphological phase systems are obtained, but two-microphase systems result above this level. This behavior is displayed by several epoxy resins. Two-phase systems display a superior balance of heat distortion temperature and impact strength, thus providing tough systems with greater elevated temperature capabilities than are obtained with single-phase systems.
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  • 48
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 751-760 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Various N-cycloalkyl fumaramides having different characters of N-cycloalkyl groups such as piperidine, morpholine, or pyrrolidone were synthesized and homopolymerized or copolymerized with styrene by use of a radical initiator and ultraviolet irradiation, respectively. N,N′-Dipiperidinyl or -dimorpholyl fumaramides copolymerized with styrene to form a random copolymer, while N,N′-fumaroyl dipyrrolidone tended to form an alternating copolymer with styrene, indicating that the electron distribution of the N-cycloalkyl group affects the polymerizability of fumaramide derivatives. Photopolymerizability of these fumaramides was not as great as that of α,β-unsaturated esters.
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  • 49
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 737-749 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(vinyl chloride) (PVC) alone or mixed with 10 wt-% and 50 wt-% TiO2, SnO2, ZnO, and Al2O3 were pyrolyzed by using a pyrolysis gas chromatograph. Benzene, toluene, ethylbenzene, o-xylene, styrene, naphthalene, and various chlorobenzenes were identified. No hydrocarbons could be detected in pyrolysis products of any samples at 200°C. More aromatic hydrocarbons than aliphatic hydrocarbons are released from the PVC-TiO2 system and in preheated PVC. The contrary result is observed in the PVC-ZnO and PVC-SnO2 systems. Aromatics having methyl endgroups are easily released from the PVC-ZnO and PVC-SnO2 systems and at elevated pyrolysis temperature, because methylene groups are easily isolated along the chain by ZnO, SnO2 and the heating. The release of ethylbenzene o-xylene, and chlorobenzenes suggests a repeated dehydrochlorination and recombination of HCl and Cl2 to double bonds along the chain. Possible decomposition mechanisms of PVC are discussed.
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  • 50
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 785-792 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Maleic anhydride (MAn) was irradiated with ultraviolet light in dioxane at 35°C without initiator, and predominantly a MAn oligomer was obtained with a small quantity of cyclic dimer of MAn. Mass spectrometric, NMR, and elementary analysis investigation of the oligomer showed that it is composed of about four MAn units and one dioxane molecule per molecule.
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 799-805 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of zirconium poly-O-amidoximes was affected by using both interfacial and aqueous solution techniques. Reaction is rapid. The yield for the synthesis of analogous titanium product is Cp2ZrCl2 〉 Cp2TiCl2 which is consistent with that predicted by the hard-soft acid-base theory.
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  • 52
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 825-836 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of seven para- or meta-substituted phenylmethylbis(dimethylamino)-silane monomers has been carried out. These silanes were polymerized with 1,4-bis(hydroxydimethylsilyl)benzene in tetrahydrofuran at 30°C, and the polymerization kinetics were followed by monitoring dimethylamine evolution for 200 min. The polymers were quenched by precipitation in methanol and molecular weight data were obtained. The polymerizations followed second-order kinetics in every case as evidenced by the linear plots of 1/(a - x) versus time. The molecular weight data generally correlated with the specific reaction rate constant k2 to show an increasing polymer molecular weight with increasing polymerization rate, although the range of k2 values obtained for the substituted aminosilanes was relatively small (2.50 × 10-5-6.67 × 10-5 l./mole-sec). The value of k2 increased in the following order: p-OCH3, p-F, m-CH3, H, m-OCH3, p-CF3, 3,5-di(CF3). The logarithms of the rate constants correlated with the σ constants for the substituents, with a reaction constant, ρ of 0.391. The displacement at silicon in these reactions is discussed in terms of bimolecular mechanisms in which a four-center transition state may participate.
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  • 53
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 851-863 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N,N′-Dicaproyl (-)1,2-diaminopropane (I) was used as a convenient model for the study of the optical activity of a nylon type polyamide: polysebacamide (-)1,2-diaminopropane (II). ORD of I was measured in different solvents. A peculiar behavior is observed in methanol in the presence of mineral salts. The influence of 0.1M potassium salts (Cl-, Br-, SCN-, NO3-, SO4-2) and 0.1M alkaline chlorides and alkaline earth chloride hexahydrates on the optical activity of I in methanol are described. Alkaline salts and MgCl2 give approximately the same effect: there is a decrease of the rotations without change of sign. SrCl2 and CaCl2 shift ORD curves towards the negative rotations, the last one giving complete inversion. This inversion is directly related to the CaCl2 concentration and is attributed to adduct formation between amide groups and salt. Assuming that the different species are at equilibrium, an apparent equilibrium constant is obtained from the optical rotations for a complex of one mole of CaCl2 with one mole of I. Results are used to discuss the complex ORD of poly(-) 1,2-diaminopropane sebacamide in methanol saturated with CaCl2.
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  • 54
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 875-883 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolymers of poly(ethylene terephthalate) (PET) containing 1-24% poly(diethylene glycol)terephthalate (PDEGT) were prepared and characterized by infrared spectra. The energy and entropy of activation for the thermal degradation were measured for these copolymers and for the PDEGT. These activation energies and energies and entropies were found to decrease steadily with increasing diethylene glycol content. From these measurements the mechanism of degradation of PDEGT was found to be different from that of PET. Fibers prepared from seven different copolymeric compositions were heat-aged at 121°C and 204°C for 24 hr. From the changes observed in intrinsic viscosity, per cent ether, hydroxyl and carboxyl endgroups during heat aging it became apparent that the mechanisms for decomposition are operative below melt temperatures and can rapidly destroy such copolymers.
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  • 55
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 897-910 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of cyclopolymerization was investigated by using N-n-propyldimethacrylamide (PDMA). Completely cyclized polymers were formed on polymerization of PDMA by a radical initiator. Moreover, those copolymers of PDMA and various monomers, such as styrene, methyl methacrylate, and vinyl acetate, obtained did not contain any detectable pendent double bonds. The kinetic investigation showed that the termination reaction proceeded between the cyclized radicals. The attempted polymerization of N-n-propyl-N-isobutyrylmethacrylamide, the monofunctional counterpart of PDMA, was failed. These results appear to confirm that cyclopolymerization of PDMA proceeds through a concerted mechanism which has been proposed for the mechanism of the cyclopolymerization of various difunctional monomers. Measurement of the ESR spectra of propagating radical has, however, revealed that the rate-determining step of the cyclopolymerization of PDMA is not intermolecular propagation but intramolecular cyclization, which indicates that the cyclization reaction proceeds in a stepwise way. This apparent contradiction was explained based upon thermodynamic considerations.
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  • 56
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 925-928 
    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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  • 57
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 929-937 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of acetylene with tris(acetylacetonato)titanium(III) and diethylaluminum chloride system leads to formation of benzene, a trace of ethylbenzene, and a small amount of polyacetylene. The isotopic composition of products obtained from cyclotrimerization of acetylene-d2 and an equimolar mixture of acetylene and acetylene-d2 is investigated to elucidate the mechanism of the cyclotrimerization. The results suggest a mechanism in which an acetylene inserts into the metal - ethyl bond formed by reaction of Ti(acac)3 and Al(C2H5)2Cl, followed by insertion of two acetylene molecules and elimination of a hydrogen atom from the first inserted acetylene to yield an ethylbenzene and a metal hydride intermediate. The metal hydride intermediate catalyzes acetylene cyclotrimerization to give benzene. During the reaction, the hydrogen atom in the metal hydride intermediate does not exchange with the hydrogen atom in the inserted acetylene molecules.
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  • 58
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 953-965 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Active hydrogen compounds such as hydroquinone (HQ), cyclohexanone (CH), acetophenone (AP), and 4,4′-methylene bis-N-methylaniline (MNA) polymerized with formaldehyde (F) and secondary diamines to produce Mannich base polyamine polymers. The HQ-containing polymers were oxidized to benzoquinone (BQ)-containing polymers and their redox properties were investigated in the desulfurization of hydrogen sulfide.
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  • 59
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 993-999 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The energy transfer behavior of an ultraviolet stabilizer, nickel dibutyldithiocarbamate (BTN), is examined in solution and in thin polypropylene films. The rate of photosensitized dissociation of this nickel chelate by 4-methyl-2-pentanone in solution was found to be approximately ten times that of its photodissociation after direct ultraviolet excitation. The rate of photodissociation of BTN in preoxidized polypropylene films was also measured. It was found that BTN does not quench the excited carbonyl groups in degassed polymer films. These results are compared to those for nondegassed preoxidized polypropylene samples and are discussed in terms of singlet oxygen quenching. A phenolic antioxidant was found to have no effect on the photodissociation of BTN in either degassed or nondegassed polypropylene films.
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  • 60
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1001-1010 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization in bulk of racemic tert-butyl thiirane with a chiral initiator resulting from the reaction between diethylzinc and (—)3,3-dimethyl-1,2-butanediol produces an optically active polymer by preferential consumption of R enantiomer. The unreacted monomer is enriched in S enantiomer. The relative rate r of consumption of R enantiomer versus S enantiomer is as high as 2.8. Obtained polymer could be separated into two crystalline fractions: an optically active fraction, formed from regular sequences of R type enantiomeric units, and an optically inactive fraction which corresponds to a racemate. Experimental results are consistent with a stereospecific mechanism of addition, the two enantiomers being chosen by two different type of sites. The stereoelective process is due to an unequal number of these two types of sites.
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  • 61
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1041-1048 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New routes for copolymerization of carbon monoxide with styrene or vinyl chloride were found by emulsion polymerization (nonionic or ionic emulsifier). These procedures yielded copolymers containing carbonyl groups even at high conversion. These carbonyl-containing polyketones were photoirradiated in solvent. In carbon monoxide - styrene copolymer of high molecular weight, the viscosity change produced by photoirradiation was especially remarkable, while in carbon monoxide - vinyl chloride copolymer no pronounced change in viscosity was observed, even at high contents of carbonyl group.
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  • 62
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1023-1039 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Torsional braid analysis was used to investigate the crosslinking behavior of linear quinoxaline polymers with and without reactive side groups. The kinetic parameter followed was the glass transition temperature during isothermal exposure in an inert atmosphere. With high molecular weight polyamide-quinoxaline copolymers (PPAQ), an initial decrease in Tg was observed during heat exposure which was followed by a subsequent increase in Tg. This was attributed to simultaneous chain scission and crosslinking reactions. Since the effect of random chain scission on the initial change in Tg of the highest molecular weight polymer samples is much stronger than on low molecular weight analogues, a Tg minimum was observed only on the highest molecular weight polymers. Because of the complexity of the reactions occurring one must consider the activation energies obtained from the Arrhenius plots as “apparent” activation energies. No attempt was made to elucidate the mechanisms of these reactions. It has been shown that isothermal heat exposure of high-temperature aromatic polymers in an inert atmosphere leads to crosslinking. In general, however, linear polymers that have reactive side groups such as methyl or carboxyphenyl groups along the polymer chain crosslink more rapidly than the analogs without these groups.
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  • 63
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1493-1503 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Crystals of the trans-octahedral complex Co(4-Vpy)4(NCS)2 on being heated below the melting point decompose with liberation of 4-vinylpyridine (Vpy) and concurrent polymerization of the free monomer. The two reactions have been followed by differential scanning calorimetry, thermogravimetry, and optical microscopy. Polymerization is inhibited by inclusion of hydroquinone during recrystallization of the complex. This has allowed the kinetic analysis of the decomposition and polymerization to be simplified. Isothermal mass-loss determinations under reduced pressure (10-2 torr), at various temperatures in the range 120-160°C, on hydroquinone-inhibited crystals corresponded to the loss of up to three molecules of vinylpyridine per molecule of starting complex. With uninhibited crystals over the same temperature range the total number of ligands lost was approximately two with a marked decrease near 175°C owing to rapid polymerization. Isothermal decomposition curves for inhibited and uninhibited crystals approximated to the Avrami-Erofeev equation. Values of n varied with temperature. Activation energies for decomposition and polymerization for both types of crystal were estimated from Arrhenius plots.
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  • 64
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1505-1513 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of gas-phase singlet molecular oxygen (1ΔO2) upon several solid polymers was investigated by using electron paramagnetic resonance, infrared spectroscopy, and chemical detection techniques. The study was performed by use of 1ΔO2 produced by microwave discharge. The application of this method to polymer studies was closely examined. The saturated-chain polymers polystyrene, polyurethane, and polyethylene were found to be inert within the experimental conditions to reaction with 1ΔO2, while the unsaturated polymers cis-polybutadiene, trans-polybutadiene, and trans-polyisoprene were found to react quite readily in an apparently surface or near-surface limited reaction to produce hydroperoxide and/or peroxide groups. The introduction by homogeneous mixing of some known metal-chelate 1ΔO2 quenchers into the polymer trans-polyisoprene appeared to significantly decrease the rate of oxidation observed.
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  • 65
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1531-1539 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The degradation of a series of polybenzimidazoles containing metylene groups in the chain was studied by TGA and MS. On heating the polymer derived from m-phenylenediacetic acid and 3,3′-diaminobenzidine to about 560°C in argon, partial fast decomposition into a solid sublimate was observed. The sublimate consisted of a mixture of fractions derived from the breaking of the chain at the methylene bonds. These methylene groups can be preoxidized at 250°C to carbonyl groups, eliminating thereby this mode of decomposition. At temperature higher than 560°C, gaseous products similar to those of the corresponding all-aromatic PBI are obtained.
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  • 66
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1559-1564 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four new s-triazine polymers were prepared by the mercury-induced coupling of bromodifluoromethyl-substituted ditriazinyl-perfluoroalkane derivatives. Each polymer was composed of CF3-substituted s-triazin rings alternately joined with —CF2CF2—segments and \documentclass{article}\pagestyle{empty}\begin{document}$\hbox{---}\hskip-5pt({\rm CF}_2 )_8 \hbox{---}$\end{document}, a mixture of —(CF3CFO(CF2)5OCF(CF3)— and —(CF3)CFOCF2CF(CF3)OCF2)4—, —CF2OCF2—, or —CF2SCF2—, segments. All polymers were elastomeric and displayed high temperature stability on thermogravimetric analysis. The polymers containing either —CF2OCF2— or —CF2SCF2— segments showed high temperature limits slightly lower than the other two systems.
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  • 67
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1565-1567 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 68
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1173-1179 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methyl methacrylate was polymerized at 40°C with VOCl3-AlEt2Cl catalyst system in n-hexane. The rate of polymerization was proportional to catalyst and monomer concentration at Al/V ratio of 2 and overall activation energy of 9.25 kcal/mole support a coordinate anionic mechanism of polymerization. The catalytic activity and stereospecificity of this catalyst system is discussed in comparison with that of VOCl3-AlEt3 catalyst system.
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  • 69
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1203-1208 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transcrystalline films of polyethylene were studied by polarized infrared spectroscopy with varying angles of incidence. The average orientation of the unit cells in the transcrystalline structure was shown to be such that the a axes were predominantly parallel to the surface of the films, and the b axes were predominantly perpendicular to the surface.
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1209-1232 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The terpolymerization of ethylene, propylene, and methylcyclopentadienyl-5-endonorborn-2-enylmethane (III) by means of different vanadium-based coordination catalysts was investigated. The structure of III and its isomeric composition was studied by using vapor-phase chromatography, mass spectrometry, and NMR, infrared, and ultraviolet spectroscopy. The catalyst system V Acac3-Et2AlCl was used under different conditions, and the influence of several variables regulating the terpolymerization process were related to the properties of the resulting terpolymers (EPTM). The insertion of III into EPTM chains takes place randomly and does not influence the random distribution of comonomers. The selective opening of the norbornene double bond of III has been demonstrated by use of 2,3-dihydro-III as model compound. Tritiated III gave a radiochemical titer of unsaturation in excellent agreement with the value deduced from ultraviolet measurements. The influence of Lewis bases added to VAcac3-Et2AlCl catalyst is discussed.
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1233-1241 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The phosphorescence from the nylon polymers 6, 66, 11, and 12 has been studied from the aspects of excitation and emission wavelength location and of emission lifetime. In contrast to the other nylons, the 66 polymer exhibits two distinct phosphorescence bands, both of which are sensitive to thermal and photochemical oxidation of the polymer. The species responsible for these emissions are concluded to be carbonyl in nature and their role in the complex reactions that occur during thermal and photochemical oxidation of the polymer is discussed.
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1243-1255 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copper complexes and the cobalt complex with the ligand of 3-(2-pyrrolylmethyl-enimino)propene-1 (PIP) or p-(2-pyrrolylmethylenimino)styrene (PIS) were synthesized and homopolymerizations and the copolymerization with styrene, acrylonitrile, methyl methacrylate and acrylic acid studied. In the polymerization of chelate monomers, inhibition of radical polymerization by the central metal ion was observed, but the chelate polymer could be obtained only if the initiator was present in higher concentrations in the feed. It is considered that the strength of inhibition depends on the electronic configuration of d-orbitals of the central metal ion. The initiation mechanism of the cupric chelate monomer may be reduction of the metal ion by the redox reaction with a primary radical via the intramolecular electron transfer through the π-conjugated system of the ligand prior to the propagation step. This mechanism was verified by studying the redox reaction of various copper complexes with DPPH. In the system of the copper complex containing PIS and acylic acid the alternating copolymer could be obtained at any mole fraction of monomer mixture in feed.
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  • 73
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1269-1290 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ability of styrene-methyl methacrylate copolymers to stabilize silica dispersions has been investigated. Random, block, and graft copolymers covering the entire composition range have been employed in carbon tetrachloride, trichloroethylene, and benzene solutions. Equilibrium sediment volumes and dispersion turbidities provide adequate and concordant estimates of stabilization efficiency. Polystyrene is not adsorbed by precipitated silica from trichloroethylene or benzene and does not stabilize dispersions in these liquids; although adsorbed from carbon tetrachloride, there is no stabilization. Poly(methyl methacrylate) is an efficient dispersion stabilizer, and its performance is independent of molecular weight over a wide range. Random copolymers having styrene contents in excess of ca. 60% do not stabilize in trichloroethylene but do so in carbon tetrachloride, although well adsorbed in both cases. With this major exception, and that of a low-styrene graft copolymer in carbon tetrachloride, copolymers of all structures and compositions stabilize well, better than poly(methyl methacrylate) in the solvents examined. A substantial degree of surface coverage is necessary for optimum stabilization. Subsidiary solution adsorption and layer thickness measurements are also reported.
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1301-1311 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(phenylene sulfides) containing various amounts of pendant cyano groups were synthesized from m-benzenedithiol and the corresponding amounts of p-dibromobenzene and 3,5-dichlorobenzonitrile. The polymers prepared by the use of 10, 15, 20, and 25% of the nitrile-containing dichloro compound were slightly off-white with melting ranges below 100°C and had inherent viscosities of about 0.15 dl/g in hexamethylphosphoric triamide at 30°C. The polymers prepared from m-benzenedithiol and the stoichiometric amounts of 2,4-dichlorobenzonitrile or 3,5-dichlorobenzonitrile looked similar to those described above, yet they possessed much higher melting ranges. The poly(phenylene sulfide) prepared by the use of 2,4-dichlorobenzonitrile had an inherent viscosity of 0.06 dl/g while the polymer prepared from the 3,5-dichloro isomer had an inherent viscosity of 0.38 dl/g. All the polymers listed above were crosslinked by heating alone or in the presence of anthracene-9,10-bisnitrile oxide to give black resinous polymers that were insoluble in hexamethylphosphoric triamide in which the original polymers dissolved quite readily.
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1323-1325 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1337-1343 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1345-1345 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1385-1394 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactivity of 1-phenylbutadiene (1-PBD) in cationic polymerization and the monomer structure were investigated. 1-PBD polymerized at -78°C in several solvents initiated by cationic catalysts such as stannic chloride and tungsten hexachloride. The polymerizations proceeded predominantly via 3,4-type propagation mode, and gave low molecular weight polymers. More than one double bond of 1-PBD was consumed during the polymerizations, probably due to transfer and cyclization reactions. 1-PBD was several times as reactive as styrene and trans-1,3-pentadiene in copolymerizations. The Hammett plots of reactivities of ring-substituted 1-PBD in cationic polymerization gave the p-value of -1.20, which is 0.6 times that of styrene. The 1H and 13C NMR chemical shifts of ring-substituted 1-PBD were measured and discussed in relation to the reaction mechanism.
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  • 79
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1375-1383 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Changes in properties of linear aromatic heterocyclic polymers of the polyimide class after introduction of ester linkages into their dianhydride component and of the oxygen and sulfur atoms into their diamine component have been studied. Thermomechanical, dilatometric, thermographic characteristics and x-ray diffraction patterns of poly(ester amic acids) and polyester-imides have been investigated. On heating, poly(ester amic acids) and amorphous polyesterimides exhibited a peculiar effect of self-orientation of macromolecules. The x-ray diffraction patterns of unoriented films indicate that they exhibit axial-planar texture with the c axis of macromolecules in the film plane. The formation of the texture is preceded by mutual arrangement of macromolecules, i.e., by a precrystallization process beginning in the amorphous state. Because of this, on heating at temperatures ranging from 200 to 380°C, polyester-imides yield highly crystalline products. Crystallographic parameters of the polymer lattices on x-ray diffraction patterns and dichroism of absorption bands in polarized infrared spectra, the most probable conformations of macromolecules of some polyesterimides are proposed.
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  • 80
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1407-1420 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymers having stable pendant . radicals were synthesized through their precursor polymers by oxidizing them in air or by H2O2-Na2WO4. Hydrochlorides and sulfates of 4-methacryloylamino- and 4-methacryloyloxy-1-hydroxy-2,2,6,6-tetramethylpiperidines were synthesized as precursor monomers and polymerized by using α,α′-azobisisobutyronitrile under appropriate conditions to precursor polymers of high molecular weight: poly-4-methacryloylamino-/oxy-1-hydroxy-2,2,6,6-tetramethylpiperidinehydrochlorides and sulfates. The precursor polymers were converted to polymers having nitroxyl stable radicals, i.e., poly-4-methacryloylamino-/oxy-2,2,6,6-tetramethylpiperidine-1-oxyls, by oxidation in air or with H2O2-Na2WO4 without any main-chain scission. The structure of the resultant stable radical polymers was determined by infrared, ultraviolet, and ESR spectroscopy. Based on the results of spectroscopic analysis and Kjeldahl analysis, the transformation from precursors to nitroxyl stable radical polymers was found to be quantitative. Investigations on the applicability of polymeric nitroxyl radicals to oxidation-reduction reactions were attempted by means of polarography; the reduction half-wave potential was found to be -1.16 V for the mercury pool.
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  • 81
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1443-1450 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3,3-Difluorocyclobutene-1-carbonitrile (DFCB) was synthesized via cycloaddition of 1-chloro-2,2-difluoroethylene and acrylonitrile, followed by dehydrochlorination with 1,4-diazabicyclo[2.2.2]octane in tetrahydrofuran. Unlike cyclobutene-1-carbonitrile, this monomer did not homopolymerize either under radical or anionic conditions. As an electron-poor monomer it copolymerized in the presence of free radicals with electronrich monomers such as styrene in good yield. It also copolymerized with electron-poor monomers such as acrylonitrile, although in lower yields. The extent of incorporation of DFCB in the copolymers also depended on the electronic characteristics of the comonomers: high incorporation occurred with electron-rich monomers, low incorporation with electron-poor monomers. One extremely electron-poor monomer, trimethyl ethylenetricarboxylate, did not copolymerize with DFCB.
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  • 82
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1451-1460 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrolysis of poly(tert-butyl N-vinylcarbamate) at 185-200°C in bulk yields a rigid foam containing cyclic urea units, primary amine units, and a small amount of urea crosslinks. The yield of primary amine units (ca. 13%) and the yields of carbon dioxide (ca. 57%), isobutylene (ca. 57%), and tert-butanol formed in this reaction indicate that it involves pairwise decomposition of adjacent carbamate units to form cyclic urea units, tert-butanol, carbon dioxide, and isobutylene. The vinyl amine units are formed from carbamate units that become flanked by urea units. The amounts of amine units and residual carbamate units were determined as a function of degree of pyrolysis by an ion-exchange technique and agreed with values expected for a random cyclization process. The pyrolyzed polymers are useful as ion-exchange resins and as rigid foams having good thermal stability.
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  • 83
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1469-1491 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The γ-radiolysis of copolymers of ethylene and carbon monoxide (CO-PE) containing 0-9 wt-% of CO has been studied in the solid phase under vacuum with respect to hydrogen production, scission, and crosslinking. In this regard, the introduction of carbonyl groups into polyethylene increased both the scission and crosslinking efficiency. However, a theoretical statistical treatment for random scission and crosslinking, which was used to calculate G(s) and G(x) yields, predicted gelation with irradiation dose; this was confirmed experimentally. The increased G(x) values are attributed to the localization of absorbed energy in the carbonyl group arising from preferential trapping of thermalized secondary electrons. A stoichiometric balance is shown to be consistent with the reduction of one carbonyl group to a secondary alcohol per excess crosslink observed. The G(H2) yield is reduced by the presence of ketone groups to a level which is in close agreement with the yield obtained for the model ketone 12-tricosanone. This quenching of H2 production is explained by intramolecular electronic energy transfer along the chain to the carbonyl group with concomitant intermolecular charge transfer between neighboring molecules.
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  • 84
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1515-1529 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polybenzimidazoles were prepared in poly(phosphoric acid) from isophthalic, m- and p-phenylene diacetic, succinic, adipic, suberic, and sebacic acids and 3,3′-diaminobenzidine, 3,3′,4,4′-tetraaminodiphenyl ether and 3,3′,4,4′-tetraaminodiphenylmethane. The thermal, mechanical, and bonding properties were studied. A 3:1 copolymer of isophthalic and m-phenylenediacetic acid with 3,3′-diaminobenzidine showed the best results as far as isothermal oxidation resistance and thermal and processing characteristics.
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  • 85
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1541-1547 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thin films of poly(ethyl acrylate) and poly(n-butyl acrylate) were decomposed in vacuo by means of a high pressure Hg lamp, and the rate of development of volatile products was measured. The main gaseous products were CO, CO2, and the alcohol, aldehyde, alkane, and formate derived from the respective ester groups. In addition poly(ethyl acrylate) evolved acetal as well as ethyl propionate, while n-butyl valerate was evolved from poly(n-butyl acrylate) only after prolonged exposure. All products and the principal features of the decomposition are discussed.
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  • 86
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1549-1558 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermal aging of a chromocene catalyst, (C5H5)2Cr/SiO2, in an inert atmosphere leads to a modified catalyst which shows poor response to hydrogen as a transfer agent. Polyethylenes prepared at a polymerization temperature of 90°C with this modified catalyst have a low melt index and high vinyl unsaturation level. By thermogravimetry the weight loss of the catalyst, relative to dehydrated silica, was equivalent to loss of one cyclopentadienyl ligand per chromium site. Pyrolytic gas chromatography showed cyclopentadiene was liberated in the thermal process. These overall studies provide strong evidence that loss of a cyclopentadienyl ligand in supported chromium catalysts has a profound effect on overall polymerization behavior.
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  • 87
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1841-1849 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(γ-1-naphthylmethyl L- and DL-glutamate) (PNLG and PNDLG) and copolypeptides of γ-1-naphthylmethyl L-glutamate and γ-benzyl-L-glutamate were used as sensitizers for isomerization of trans-1,2-diphenylcyclopropane. Quantum yields relative to that of 1-methylnaphthalene were measured in dichloroethane (DCE) and dichloroacetic acid (DCA). The relative quantum yield in DCE was smaller than unity for PNLG, but greater than unity for PNDLG and copolypeptides. The result is discussed in terms of increased effective collisional radius and energy trapping by excimer formation. The relative quantum yields in DCA were close to unity except for the copolypeptides of higher γ-benzyl L-glutamate content. This suggests that the naphthalene groups act in the same manner as their monomeric counterparts in the random conformation and that the greater proportion of γ-benzyl L-glutamate in the copolypeptides lowers the quantum efficiency because trans-1,2-diphenylcyclopropane must penetrate through the polymeric medium in order to encounter the excited naphthalene.
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  • 88
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1851-1859 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The terpolymerization of sulfur dioxide, butene-1 and acrylonitrile affords terpolymers containing equimolar amounts of sulfur dioxide and butene-1 with various acrylonitrile contents. Ultraviolet irradiation was found to accelerate the polymerization and decrease the acrylonitrile content in the polymer. This fact is interpreted by a mechanism through a copolymerization of sulfur dioxide-butene-1 complex and acrylonitrile, whereby the polymerizability of sulfur dioxide-butene-1 complexed monomer may be accelerated by ultraviolet light. In fact, a binary system of sulfur dioxide and butene-1 was found to be accelerated by ultraviolet irradiation, and it affords a maximum rate at a 1:1 composition of feed monomer. Ultraviolet light of 250-300 mμ wavelength is effective for the initiation and the propagation. This may be ascribed to the ultraviolet absorption of the sulfur dioxide-butene-1 complex. The temperature coefficient was measured in both dark and ultraviolet irradiation reactions. The ultraviolet irradiation enhances the reactivity of sulfur dioxide-butene-1 complexed monomer at low temperature. In the terpolymerization with sulfur dioxide, isoprene, and butadiene, the ratio of isoprene and butadiene in the terpolymer was not altered by ultraviolet irradiation because both monomers from complexes with sulfur dioxide, perhaps having the same temperature coefficient for the polymerization.
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  • 89
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1881-1886 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A. study on the kinetics of gas-phase copolymerization of formaldehyde and 1,3-dioxolan effected by stannic chloride in a flow reactor with ideal mixing is reported. Equations were calculated describing the run of process depending on the composition of the outgoing flow measured with a gas chromatograph. It was established that the reaction takes place under stationary conditions. The change of the degree of conversion of monomers, and composition of the stable portion of the copolymer, and copolymer molecular weight with catalyst concentration was examined. It was shown that a kinetic and diffusion area may be possible. A product of high molecular weight and thermostability was obtained. The molecular size distribution was ascertained to be close to the exponential type. The average number of blocks and units of both monomers was calculated. Different posteffects for the two reacting substances were found.
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  • 90
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1905-1912 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two isomeric forms of active chain ends were observed simultaneously in the living cationic polymerization of tetrahydrofuran (THF) initiated with derivatives of trifluoromethanesulphonic acid (CF3SO2OH). These forms are the macroion and the macroester. Concentrations of both species were determined in the polymerization of THF conducted in CCl4, CH2Cl2, and CH3NO2, by using 300 MHz 1H NMR spectroscopy. In CCl4 the macroester form dominates (96%), and in CH3NO2 only 8% of macroester could be detected. In CH2Cl2 both species coexist in comparable concentrations ([macroion]:[macroester] = 1:3). The present direct measurements are in agreement with our previous determination of the proportions of macroester and macroions based on kinetics data. Therefore, this also confirms our earlier conclusion, that if an equilibrium between the macroions and macroester is involved in the polymerization of THF, the chain growth proceeds almost exclusively on the macroions.
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  • 91
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1925-1931 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of polyphenylquinoxalines has been synthesized by the reaction of p,p′-oxydibenzil with aromatic tetraamines containing varying numbers of fused rings. It was found that the glass transition temperatures of the resultant polymers increased as the the number of adjacent fused rings in the polymers was increased. This provided the basis for achieving glass transition temperatures for the polymers in excess of 400°C, substantially higher than the state-of-the art polyphenylquinoxalines. All of the polymers displayed both the good thermal stability and the solubility in m-cresol characteristic of the polyphenylquinoxaline family of polymers.
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  • 92
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1953-1964 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The regions trapping allyl radicals in irradiated polyethylene and the reactivity of the radicals with various monomers have been studied by electron spin resonance. Most of the allyl radicals are trapped in defects or surfaces of the crystallite, and only 10% of the radicals are trapped inside the crystallites. Since the reactivity of the allyl radicals depends on whether they come in contact with reactive monomers, the rate of reaction is related to the concentration of the monomers. When grafting reactions are initiated by allyl radicals, the rate of initiation is rapid and the rate of termination at the initial stage is also very fast. Consequently the yield of grafting increases at the initial stage but soon levels off, which is in contrast to the grafting behavior with alkyl radicals.
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  • 93
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1983-1990 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,2,2,2-Tetrachloroethyl esters of β-vinylacrylic, muconic, and fumaric acids were prepared by the addition reaction of chloral with pentadienoyl chloride, hexadienedioyl chloride, and fumaroyl chloride in the presence of FeCl3. The homopolymer of the first and copolymers of the other esters with styrene were obtained by radical polymerization. The basic chemical and physical characteristics of the compounds prepared were determined, and the assumed structure was confirmed by the infrared, NMR, and mass spectra.
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  • 94
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2005-2016 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyamides were prepared from linear, aliphatic dicarboxylic acids of six to twelve carbon atoms with 1,4-cyclohexanebis(methylamine), 1,4-cyclohexanebis (ethylamine), p-xylylenediamine, and p-phenylenebis(ethylamine). Melting points, glass transition temperatures, densities, and moisture regains were compared for the polymers to determine the relative effect of the cyclohexylene and phenylene linkages. While polyamides containing the trans-cyclohexylene group possessed higher glass transition temperatures than their aromatic counterparts, melting behavior was not as consistent. The odd-even rule, which states that polyamides with an even number of methylene linkages between the ring and the functional group melt higher than those with an odd number of such linkages, was violated in the cycloaliphatic systems. The Tg of ring-containing polyamide fibers was not dependent solely upon ring concentration, but was influenced by the molecular fit of the ringed intermediate in the polymer chains. Molecular fit appears to affect the Tg and melting point of alicyclic polyamides to a greater extent than the aromatic analogs. Differences in Tg, both within and among the polymer series, was not explained by either density or the degree of crystallinity.
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  • 95
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2035-2043 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polystyrenes having both modified and unmodified endgroup structures were synthesized. These polystyrenes were then subjected to dynamic mechanical testing below their glass transition temperature. The modified structures were shown to influence the β transition of polystyrene. While the mechanism of this secondary transition has been speculated but never unequivocally substantiated in the past, the evidence presented here strongly support the idea that the β transition of polystyrene arises from chain-end motions.
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  • 96
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2045-2052 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene, the dose rate dependence, the effect of emulsifier concentration, and the effect of monomer composition were studied. The rate of polymerization was proportional to the 0.90 power of the dose rate and the 0.26 power of the emulsifier concentration. The degree of polymerization was independent of the dose rate and the emulsifier concentration. Both the rate of polymerization and the degree of polymerization increased with tetrafluoroethylene content in the monomer mixture. The resulting copolymer was an alternating polymer over a wide range of monomer composition. It was concluded from the dose rate dependence of the rate of polymerization that the emulsion copolymerization is mainly terminated by degradative chain transfer of the propagating radical to propylene.
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  • 97
    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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  • 98
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1829-1839 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of the oxidation of poly(vinyl alcohol) (PVAL) by potassium persulfate (KPS) in aqueous solutions showed that the decomposition of KPS was greatly enhanced by the presence of PVAL, its hydroxyl groups being oxidized to ketones in a yield of about one mole of ketone from one mole of KPS. The decomposition rate of KPS was found to be given by the equation, -d[S2O82-]/dt = k[S2O82-] [PVAL]1/2, which was essentially the same as in the oxidation of alcohols of low molecular weight by persulfate ion. The occurrence of gelation of PVAL solutions and graft copolymerization of methyl methacrylate (MMA) onto PVAL in the presence of KPS was evidence for PVAL radical as an intermediate species in the oxidation of PVAL. A characterization study was also carried out for the reaction products of the graft copolymerization of MMA onto PVAL with KPS in dimethyl sulfoxide solution.
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  • 99
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2087-2090 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
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  • 100
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    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2099-2103 
    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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