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  • 201
    Electronic Resource
    Electronic Resource
    Monte Carlo study of defect fluctuations and reptation in polymer melts (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 14 (1976), S. 1671-1682 
    Details
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Defect fluctuations in highly distorted polymer chains were simulated by Monte Carlo calculation. The NMR autocorrelation function was derived and described by the superposition of three exponential functions with time constants spread over two orders of magnitude. As a consequence of defect diffusion, longitudinal chain diffusion (reptation) can be expected in polymer melts. By simulating the mean-square displacement of a segment, it was found that after sufficiently long times, compared with defect density correlation times, a linear relationship holds fairly well. As a rule of thumb, it can be stated that the linear Einstein equation is valid for times much greater than 103 mean step times in practical cases (chain length: several thousand segments, defect concentration: 10-20%), or, in other words, for mean-square displacements greater than a few diffusion step lengths. A long-time chain-diffusion coefficient depending on the molecular weight and on the defect concentration could be derived. Effects on the low-field NMR relaxation behavior are derived and discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.180140912
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  • 202
    Electronic Resource
    Electronic Resource
    Studies on propagating species in cationic polymerization of styrene derivatives by acetyl perchlorate or iodine. I. Bimodal molecular weight distribution of polymers produced by acetyl perchlorate or iodine (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1089-1095 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To investigate the nature of the propagating species in cationic polymerization of para-substituted styrenes, p-chlorostyrene (pCIS), p-methylstyrene (pMS), and p-methoxystyrene (pMOS), were polymerized with acetyl perchlorate or iodine in various solvents at 0°C, and the molecular weight distribution (MWD) of the polymers was measured by means of gel-permeation chromatography. When ClO4- was a counterion, poly(pCIS) having a bimodal MWD was produced, while polymers of pMOS and pMS possessed a unimodal MWD, regardless of the solvent polarity. When more nucleophilic I- (or I3-) was a counterion, however, polymers having a bimodal MWD were produced from pMOS and pMS. These results showed that either dissociated or nondissociated propagating species existed in the cationic polymerization of styrene derivatives with acetyl perchlorate or iodine, and that the type of MWD was strongly dependent on the stability of the growing cation and the nucleophilicity of the counterion.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140506
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  • 203
    Electronic Resource
    Electronic Resource
    Electropolymerization of aminophthalic acids. I. Polymerization of 4-aminophthalic acid (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1137-1150 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4-Aminophthalic acid has been polymerized in almost quantitative yield to low molecular weight polymer by electrochemical initiation at a platinum anode. Systems involving the acid, amine salt, and the ammonium salt have been explored; the acid and/or the amine salt of the acid provides the best means of obtaining polymer. Maximum molecular weight is attained in a very short time at low current densities (∼2 hr at 50 mA). Thermogravimetric data indicate a temperature stability comparable to polyamide-imide polymers (400°C). Long reaction times and high current densities decrease molecular weight and polymer yield.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140511
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  • 204
    Electronic Resource
    Electronic Resource
    Structure and reactivity in cationic polymerization of butadiene derivatives. IV. 1-alkoxybutadienesFor Part III of this series, see Masuda et al.1 (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1157-1166 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactivity of trans-1-alkoxybutadienes in cationic homopolymerization and copolymerizations and structure of the polymers produced were investigated. 1-Ethoxybutadiene is polymerized easily at -78°C by various acidic catalysis. The reactivity of 1-ethoxybutadiene was similar to that of ethyl vinyl ether. The polymers produced possessed molecular weights of several thousands, and were composed of 70-95% 1,4 structure and 5-30% 3,4 structure. In the copolymerization of ethyl vinyl ether (M1) with 1-ethoxybutadiene at -78°C in toluene by boron trifluoride diethyl etherate, r1 = 1.15, r2 = 2.62. From the Hammett plot of the relative reactivities of alkoxybutadienes (alkoxy: CH3O, C2H5O, i-C3H7O), the reaction constant p* was determined to be -2.9. Results of the present study were compared with those of various butadiene derivatives.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140513
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  • 205
    Electronic Resource
    Electronic Resource
    Effect of comonomer sorption on radiation-induced copolymer grafting onto polyethylene and EVA films in the vapor phase (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1175-1182 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radiation-induced copolymer grafting of acenaphthylene and maleic anhydride onto polyethylene or EVA film in the vapor phase was carried out and the effect of comonomer sorption on the grafting was studied. When polyethylene film was used as a backbone polymer, the sorption of the binary monomers during the grafting increased linearly as the grafting reaction proceeded. The marked increase was probably caused by the formation of a grafted layer. Particularly, the sorption of maleic anhydride was brought about by the existence of a grafted layer. In grafting onto EVA film, the content of maleic anhddride in the grafted copolymer increased with the increasing content of vinyl acetate in EVA. Continuous measurements of sorption of the comonomers onto EVA and grafted EVA films were carried out by use of an electrobalance. The distinctive feature of the sorption was that the equilibrium sorption of acenaphthylene or maleic anhydride onto the grafted EVA film increased and the diffusion constants for both comonomers decreased markedly with increasing percentage of graft. The copolymer grafting was explained from these results by assuming that the monomer molecules are supplied to the propagating chain ends mostly through a sorbed state on the polymer film.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140515
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  • 206
    Electronic Resource
    Electronic Resource
    Polycondensation of mono- and difunctional derivatives of p-xylene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1241-1247 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new method for the production of polydimethylbenzylenes,$ \rlap{--} [{\rm C}_6 {\rm H}_4 ({\rm CH})_2 {\rm CH}_{\rm 2} \rlap{--} ]_n $, involves the polycondensation of the mono- and dichloromethyl and mono- and diacetoxymethyl derivatives of p-xylene via an acid-catalyzed reaction in anhydrous acetic acid. The reaction of the difunctional derivatives is slower than the reaction of the monofunctional ones, leading to linear, predominantly crystalline, high-melting polymers with molecular weights of 2000-3000. Polycondensation of both monomers under different feed ratios leads to polymers with the same structure, and the monofunctional monomers condense with themselves more favorably than with the difunctional ones. Thus a head-to-head structure is preferred, and crystalline polymers of high structural purity are obtained.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140523
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  • 207
    Electronic Resource
    Electronic Resource
    Short branching in poly(vinyl alcohol). III. Some properties of model polymers of short-branched poly(vinyl alcohol) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1267-1275 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Melting point, the iodine color reaction, and foam fractionation were studied on model poly(vinyl alcohol) (PVA) having short branches of one or two monomer units in length. An increase in the amount of short branching units caused a marked decrease in color intensity of the PVA-iodine reaction and in the melting point. These tendencies were more remarkable when the short branching was two monomer units in length than when it was one monomer unit. It was also found that foam fractionation of an aqueous PVA solution produced PVA fractions with different degree of short branching, the degree increasing with increase in the fraction number. The color intensity of the PVA-iodine reaction has been confirmed to decrease with increase in the fraction number, but this result cannot be explained solely in terms of the short branching. It is concluded that the phenomenon of foam fractionation of PVA and the iodine color reaction of the fraction appear to be governed by many factors such as molecular weight, stereoregularity, and short branching.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140526
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  • 208
    Electronic Resource
    Electronic Resource
    Some properties of polyethylene produced by radiation polymerization at -78°C (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1293-1295 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140530
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  • 209
    Electronic Resource
    Electronic Resource
    19F- and 1H-NMR spectra of tetrafluoroethylene-propylene copolymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1317-1330 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High resolution 94-MHz 19F- and 100-MHz 1H-NMR spectra were measured on a series of tetrafluoroethylene (TFE)-propylene (P) copolymers having a range of composition (TFE/P molar ratio = 37/63-55/45) and polymerized at different temperatures (-23, 25 and 65°C). The spectra were analyzed in relation to copolymer compositions. The assignment of 19F resonance in terms of tetrads proposed previously was confirmed, and the tentative assignment of 1H resonances was proposed in terms of triads. The spectra thus interpreted revealed the sequence distribution of the copolymers. Copolymer compositions calculated from NMR spectra and elemental analysis agreed rather well with each other. Monomer reactivity ratios were calculated from the sequence distributions and compared with those obtained from the elemental analysis. It was observed that highly alternating copolymers are obtained in this system over a wide range of monomer composition at lower temperatures and that a deviation from alternancy increases slightly with rising polymerization temperature.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140602
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  • 210
    Electronic Resource
    Electronic Resource
    Hydrogen-transfer polymerization of methyl-substituted acrylamides (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1347-1361 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Base-catalyzed hydrogen-transfer polymerization and copolymerization of acrylamide and its methyl-substituted derivatives were studied in pyridine at 110°C. n-Butyllithium was used as an initiator. The observed rates of these homopolymerizations were found to decrease in the following order: acrylamide 〉 crotonamide 〉 methacrylamide 〉 N-methylacrylamide 〉 N-methylcrotonamide 〉 tiglinamide 〉 N-methylmethacrylamide ≫ α-chlorocrotonamide ≃ α-cyanocrotonamide = 0. Acrylamide gave the polymer with the highest degree of polymerization among the monomers examined. It was found that the number and the position of the methyl substituent in acrylamide affected significantly both the rate of polymerization and the molecular weight of the polymer. Although all polymers obtained, except the N-methyl derivatives, contained both methanol-soluble and methanol-insoluble fractions, a polyamide structure with unsaturated terminal monomer unit was confirmed by both infrared and NMR determinations. From the NMR determination of the saturated and terminal unsaturated units, the degree of polymerization of the resulting polyamides were also obtained. The monomers were also found to copolymerize by a hydrogen-transfer mechanism. However, the main chain of the resulting copolymers was composed of the more reactive monomer unit, and the less reactive monomer was incorporated only as a terminal unit when a less reactive monomer was copolymerized with a more reactive one. From these results, it was concluded that these polymerizations proceeded via an intermolecular hydrogen-transfer mechanism (i.e., stepwise mechanism).
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140605
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  • 211
    Electronic Resource
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    Effect of valence state of vanadium on stereoblock polymerization of methyl methacrylate with VOCl3-AlEt2Br catalyst system (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1397-1402 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of methyl methacrylate with the VOCL3-ALEt2Br catalyst system in n-hexane has been studied. The first-order dependence of rate of polymerization on catalyst and monomer concentrations, activation energy of 6.67 kcal/mole, and NMR spectra of polymer lend support to a coordinate anionic mechanism of polymerization. It has been shown that the vanadium in V+2 oxidation state is less active than V+3 oxidation state of active complex.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140608
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  • 212
    Electronic Resource
    Electronic Resource
    Effect of isotopic composition on free-radical reactions in polyolefins (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1419-1427 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On substitution of hydrogen by deuterium the radiation yield of free radicals in polyolefins decreases ca. 2-fold. Under ultraviolet illumination (γ 〈 300 nm) in deuterated polyethylene (DPE), allyl radicals are converted into alkyl radicals (hfs constants aDα = 3.2 Oe, aDβ = 4.4 Oe); in deuterated polypropylene (DPP), allyl and peroxide radicals are converted into alkyl radicals (aDβ = 3.7 Oe). At 77°K under ultraviolet light in γ-irradiated polyethylene (PE) and DPE, triene, tetraene, dienyl, trienyl, and tetraenyl radicals are formed. Deuterium substitution has no effect on absorption spectra of polyenyl radicals and polyenes. In polyolefins the quantum yields of photochemical reactions of allyl and peroxide radicals are 0.1-1.0. Photochemical reactions of peroxide radicals result in a radical concentration increase of ca. 3-fold. In reactions of peroxide radicals in the dark, a kinetic isotope effect has been observed. Activation energies of substitution reactions of peroxide radicals are in PE, 9.3 ± 0.3 kcal/mole; in DPE, 10.2 ± 0.3 kcal/mole; in PP, 12.7 ± 0.4 kcal/mole; in DPP, 14 ± 0.5 kcal/mole. Possible mechanisms of the effect of polyolefin isotope composition on radical formation by high energy irradiation as well as on photochemical and dark reactions of free radicals are discussed. The effect of the energy released from phototransformations and radiationless deactivation of macroradicals on the migration of free valence is also considered.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140610
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  • 213
    Electronic Resource
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    Siloxane-modified heterocyclic polymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 83-92 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fully aromatic, siloxane-modified polybenzimidazoles and polybenzoxazoles were prepared by a single-stage melt polymerization and characterized. These polymers, which have good solubility in pyridine and N-methylpyrrolidinone, undergo thermooxidative decomposition above 300°C. Model compounds for these two classes as well as polypyromellitimides were also prepared.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140108
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  • 214
    Electronic Resource
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    Homogeneous polyblend of poly(vinyl chloride) with α-methylstyrene-methacrylonitrile-ethyl acrylate terpolymer (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 123-127 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Blends of poly(vinyl chloride) (PVC) and α-methylstyrene-methacrylonitrile-ethyl acrylate (AMS-MAN-EA) terpolymer have been prepared and properties studied. The polyblends are unusual inasmuch as they are transparent and possess a single glass transition; therefore, they are homogeneous. The single Tg suggests a single-phase system. The polyblends exhibit rarely observed polymer-polymer compatibility.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140112
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  • 215
    Electronic Resource
    Electronic Resource
    PolyimidothioethersPaper presented in part at the 164th Meeting, American Chemical Society, New York, August 1972. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 159-182 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The condensation of maleimide compounds with hydrogen sulfide and bisthiols was studied in several model systems. Bismaleimide compounds undergo rapid, exothermic polymerization with thiol-containing compounds in dipolar and basic solvents to give crosslinked polymidothioethers. Effective supression of the crosslinking reaction was achieved by carrying out the polymerization in the presence of a proton donor to inhibit anionic polymerization. A number of linear polyimidothioether homopolymers and copolymers were prepared and a study was made of their properties.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140116
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  • 216
    Electronic Resource
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    Copolymerization of trioxane with cyclic acetals. Effect of catalyst on polymerization and monomer reactivity (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 143-151 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymerization of trioxane with cyclic acetals, viz., 1,3-dioxolane, m-dioxane, and 4-methyl-m-dioxane, have been investigated. Three types of catalyst have been employed: a metal chelate, MoO2(AcAc)2; a Lewis acid, BF3·Bu2O; and an ion-pair, It has been ascertained that, in agreement with the previous results on copolymerization of trioxane and ethylene oxide,1 both the polymerization kinetics and the monomer reactivity have been found to be influenced by the catalyst employed. In copolymerization with 1,3-dioxolane, both BF3·Bu2O and have been found to give high molecular weight copolymers with high incorporation of 1,3-dioxolane. However, contrary to the results obtained in copolymerization with ethylene oxide, higher rate and yield have been obtained with BF3·Bu2O, making it a superior catalyst. In copolymerization with m-dioxane, has been found to be a superior catalyst to the others yielding high molecular weight copolymers with high incorporation of m-dioxane. In copolymerization with 4-methyl-m-dioxane, MoO2(AcAc)2 has been found to be an overall superior catalyst to the others. Higher rate, yield, and comonomer incorporation have been obtained using MoO2(AcAc)2 as catalyst, although somewhat higher molecular weight copolymers have been obtained with
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140114
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  • 217
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    Polymerization of coordinated monomers. IX. Charge-transfer spectrum of the system composed of metal halide, polar vinyl monomer, and electron-donating monomer (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 183-194 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 1:2 stannic chloride-methyl methacrylate complex, the 1:2 stannic chloride-acrylonitrile complex, the ethylaluminum dichloride-methyl methacrylate complex, and the ethylaluminum dichloride-acrylonitrile complex exhibit charge-transfer absorption bands in the wavelength region longer than 300 nm with electron-donating compounds such as mesitylene, styrene, toluene, and butadiene. The absorption spectrum of the mixture of either methyl methacrylate or acrylonitrile with the electron-donating compound is, however, a superpostion of the spectra of the components without any additional absorption. Methyl isobutylate, 3-butenyl methyl ketone, and propionitrile show no charge-transfer absorption bands with the electron-donating compound, even in the presence of a metal halide. Both the presence of the C-C double bond conjugating with the polar group and the coordination of the polar group to a metal halide are essential for an electron-accepting monomer to exhibit a charge-transfer absorption with the electron-donating compound. Continuous variation plots with the use of the charge-transfer band definitely show a 1:1 interaction between the methyl methacrylate coordinated to stannic chloride and styrene, resulting in the determination of the equilibrium constants for the charge-transfer complex formation in methylene chloride: 0.21 l./mole at 25°C and 0.67 l./mole at -50°C. The charge-transfer absorption is attributed to a ternary molecular complex composed of a metal halide, a polar vinyl monomer, and an electron-donating monomer.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140117
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  • 218
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    Study of radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. V. Effects of p-benzoquinone and dose rate on methyl methacrylate-silica gel system (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 275-286 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to elucidate the mechanism of radiation-induced polymerization of methyl methacrylate adsorbed on silica gel, the effects of p-benzoquinone addition and dose rate were studied in detail. Most of the polymerization is inhibited by p-benzoquinone at levels above 10-2 mole/l. The GPC spectra of both graft polymers and homopolymers show two peaks. The high molecular weight material appears to have been formed by polymerization by a radical mechanism, because these peaks decrease as p-benzoquinone concentration increases; on the other hand, their low molecular weight polymers seem to be products of an ionic polymerization mechanism because those peaks are almost not affected by p-benzoquinone. The four GPC peaks differ in dose rate dependences of their polymerization rate. The dose-rate exponents of polymerization rate were obtained for the four GPC peaks. The behavior of the low molecular weight peaks of graft polymers and homopolymers were quite different, suggesting that the polymers differ considerably in formation mechanism.
    Additional Material: 18 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140201
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  • 219
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    Polymerization of coordinated monomers. X. Kinetic study of alternating copolymerization of methyl methacrylate and styrene with stannic chloride in dichloroethane (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 307-318 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The alternating copolymerization of methyl methacrylate with styrene with the use of stannic chloride was kinetically examined at -20°C in 1,2-dichloroethane both under photoirradiation and with radical initiator (2:1 tri-n-butylboron-benzoyl peroxide system). At conversions lower than 7%, the conversion increases linearly to the polymerization time, whereas the degree of polymerization is constant irrespective of the polymerization time. The alternating copolymerizations are 1.5 order and the 1.0 order reactions with respect to the ternary molecular complex composed of stannic chloride, methyl methacrylate, and styrene, under photoirradiation and with initiator, respectively. The linear dependences of the rates upon the 0.5 order of the intensity of the incident light and upon the 1.0 order of the concentration of tri-n-butylboron indicate a bimolecular termination. The rate normalized by the 1.5 order of the concentration of the coordinated methyl methacrylate and the rate normalized by the concentration of the coordinated methyl methacrylate are proportional to the 1.5 and 1.0 orders of the charged concentration of styrene, for the copolymerizations under photoirradiation and with initiator, respectively. The kinetic results in the 1,2-dichloroethane solution are quite consistent with those in the toluene solution. The alternating copolymerization mechanism, in which the ternary molecular complex predominantly homopolymerizes as a monomer unit, is confirmed.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140204
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  • 220
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    Short branching in poly(vinyl alcohol). II. NMR spectroscopy of model polymers of short-branched poly(vinyl alcohol) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 759-766 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to develop a method of measuring the amounts of short branches in PVA, an NMR study was made of a model poly(vinyl alcohol) having short branches, one or two monomer units in length. Detection and estimation of the short branches were shown to be possible by using the 13C-NMR spectra of PVA and the 1H-NMR of acetylated PVA. In the 19F-NMR spectra of trifluoroacetylated model PVA, the resonance peaks of primary and tertiary alcohols in the branching structure were not well resolved from that of secondary alcohol of the main chain.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140323
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    Oligomerization of ethylene by tertiary butyllithium-N,N,N′,N′-tetramethylethylenediamine (TMEDA) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 773-776 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140325
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    ESR study of linear aliphatic oligoesters under γ-irradiation. I. Paramagnetic species produced in the material by irradiation at 77°K (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 813-824 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Paramagnetic species produced in a series of linear aliphatic oligoesters $ [\bond;{\rm O}\bond;({\rm CH}_{\rm 2} {\rm )}_m\bond;{\rm O}\bond;{\rm CO}\bond;({\rm CH}_{\rm 2} {\rm )}_n\bond;{\rm CO\rlap{--} ]}_P $ by γ-irradiation at 77°K was investigated by an ESR method. A predominant doublet observed immediately after γ-irradiation, which has hyperfine splitting of 20-23 gauss, is attributed to a radical anion III. Slight decay of this radical anion is observed by illuminating the sample with visible light at 77°K. A small amount of the radical anion is converted to double triplet, which is assigned to —(ES)—CH—CH2— (where ES denotes the ester group), from the result of heat treatment. The conformational angles for the two β-protons in the (6,2) oligoester are determined to be θ1 = θ2 = 30°.
    Additional Material: 6 Ill.
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    Sulfur-containing vinyl monomers. XIII. Cationic copolymerizations of vinyl sulfides with some vinyl monomers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 845-861 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cationic copolymerizations of vinyl sulfides (VS) with some vinyl monomers with boron tri-fluoride-diethyl etherate catalyst were investigated to evaluate their monomer reactivities. The effects of VS on the copolymer yield and viscosity of the resulting copolymers revealed the inhibition or retardation mechanism which was explained in terms of the formation of a stable vinylsulfonium salt by the reaction between a propagating carbonium ion and VS monomer. From the results of copolymerizations of phenyl vinyl sulfide (PVS) with isobutyl vinyl ether (IBVE), β-chloroethyl vinyl ether (CEVE), α-methylstyrene (α-MeSt), and styrene (St), the relative reactivities of these monomers were found to be in the following order: IBVE 〉 CEVE 〉 PVS 〉 α-MeSt 〉 St. The relatively higher reactivity of PVS than St derivatives was explained on the basis of the conjugative and electron-donating nature of the VS monomer. The effects of alkyl and para-substituted phenyl groups in vinyl sulfides on their reactivities toward the propagating carbonium ion were correlated with polar factors and compared with those of the hydrolysis of α-mercaptomethyl chlorides. The transition state for the propagation reaction in cationic polymerization of VS was proposed to be a π-complex type structure.
    Additional Material: 13 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140406
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    Role of polymer ligands in the oxygenation of metal chlorophyllins (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 911-922 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to obtain information about the characteristics of polymer-(metal chlorophyllins), their redox and oxygenation reactions were studied. Complexes composed of metal chlorophyllins (MChn) and partially quaternized poly(4-vinylpyridine) (QPVP) exhibited an increased stability due to electrostatic interaction between polymer cation and carboxylate anions of side groups in the MChn. The reduction of these polymer complexes by S2O42- occurred easily with an decrease in their apparent reduction potentials. The resulting low-valence complexes had an ability to absorb molecular oxygen. The oxygenation of these polymer complexes was not completely reversible; however the rate of the irreversible reoxidation was less by a factor of 1010 for the polymeric complex than that for the monomeric MChn-pyridine complex. The stability of these oxygen complexes is discussed in relation to the hydrophobicity of QPVPs.
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    Studies in ring-opening polymerization. IV. Thermal polymerization of phenyl-substituted 1,3-dioxolan-2,4-diones (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 949-960 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of C-5 phenyl substituents on the thermal decomposition of the 1,3-dioxolan-2,4-dione ring has been examined. Unlike the dimethyl-substituted ring, 5-methyl-5-phenyl-1,3-dioxolan-2,4-dione decomposes smoothly in dry nonhydroxylic solvents to yield polymer and carbon dioxide. The introduction of a second C-5 phenyl substituent produces a similar but more rapid decomposition, with the added complication of a competing ring fragmentation leading to ketone formation. An analogy is drawn between the observed behavior of the phenyl-substituted 1,3-dioxolan-2,4-diones and that of the previously studied 1,3,2-dioxanthiolan-4-one 2-oxides. These monomers therefore provide another example of the thermal polymerisation mechanism first observed with 5,5-dimethyl-1,3,2-dioxathiolan-4-one 2-oxides. In these reactions the rate-determining step is the first-order ring-scission process leading to the formation of an α-lactone intermediate. This intermediate then takes part in a very rapid chain-growth process which governs the characteristics of the polymer formed.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140415
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    Photopolymerization of methyl methacrylate and some other vinyl monomers with the use of a pyridine-bromine charge-transfer complex as photoinitiator (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 981-991 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of MMA was carried out under visible light (440 nm) with the use of pyridine-bromine (Py-Br2) charge-transfer (CT) complex as the photoinitiator. Initiator exponent and intensity exponent were 0.5 and 0.43, respectively, and the monomer exponent was found to be dependent on the nature of the solvent or diluent used. The Polymerization was inhibited in the presence of hydroquinone, but oxygen had very little inhibitory effect. An average value of kp2/kt for this polymerization system was 1.19 × 10-2, and the activation energy of photopolymerization was 4.95 kcal/mole. Kinetic data and other evidence indicate that the overall polymerization takes place by a radical mechanism. With Py-Br2 complex as the photoinitiator, the order of polymerizability at 40°C was found to be MMA, EMA ≫ Sty, MA.
    Additional Material: 7 Ill.
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    Radiation copolymerization of vinylene carbonate with isobutyl vinyl ether (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1045-1049 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radiation-induced copolymerization of vinylene carbonate (M1) with isobutyl vinyl ether (M2) has been investigated over the temperature range of 40-80°C. The monomer reactivity ratios r1 and r2 were determined to be 0.118 and 0.148, respectively, and an activation energy of 7.6 kcal/mole (31.8 kJ/mole) was calculated for the copolymerization process.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140501
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    Cleavage of poly(vinyl alcohol) in the presence of tert-butyl hydroperoxide and biologically active metal complexes (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1083-1087 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cleavage of poly(vinyl alcohol) in dimethyl sulfoxide at 42°C has been measured viscometrically in the presence of tert-butyl hydroperoxide and metal complexes. Phthalocyanine complexes of copper(II), iron(III), cobalt(II), and vanadium as VO(II) as well as hemin, hematin, chlorophyllin, and cytochrome c were used. The rates of decomposition of tert-butyl hydroperoxide in the presence of these metal complexes were measured idometrically. These data are compared to results obtained with other metal complexes in similar reactions.
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    Synthesis of polyamides by ring-opening polyaddition of benzobis[1,2]oxazinediones with aliphatic diamines (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1127-1135 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Novel oxime-containing polyamides have been prepared by the ring-opening polyaddition of combinations of two benzobis[1,2]oxazinediones, 4,6-diphenylbenzo[1,2-d:5,4-d′]bis[1,2]oxazine-1,9-dione and 4,9-diphenylbenzo[1,2-d:4,5-d′]bis[1,2]oxazine-1,6-dione, with two aliphatic diamines in a polar aprotic solvent such as N-methyl-2-pyrrolidone. The polymerization was almost completed within a day at room temperature. These polymers had inherent viscosities in the range of 0.12-0.38 and were soluble in a wide range of solvents, including formic acid and hot m-cresol, as well as a number of polar aprotic solvents. All the polymers softened at a temperature ranging from 165 to 185°C. Thermal characterization of the polyamides by TGA and DTA showed polymer decomposition temperatures of about 240°C in air.
    Additional Material: 3 Ill.
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    Polyamides from perchloro-4,4′-dichloroformylbiphenyl (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1167-1174 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New thermally stable polyamides were prepared by low-temperature polycondensation in N,N-dimethylacetamide from perchloro-4,4′-dichloroformylbiphenyl and various aromatic and aliphatic diamines. The polymers were characterized by infrared spectroscopy, elemental analysis, TGA, and DSC and found to show higher thermal stability than other nonchlorinated polyamides.
    Additional Material: 3 Ill.
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    Equilibrium anionic polymerization of n-valeraldehyde (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1221-1228 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper describes an anionic polymerization of n-valeraldehyde (VA) in tetrahydrofuran (THF) initiated by benzophenone-monolithium complex in a high vacuum system. In spite of the deposition of the resulting polymer an equilibrium state between the monomer and the polymer was observed at a temperature range of -90 to -68°C. From the linear relationship between the equilibrium monomer concentration and the polymerization temperature, values of -5.3 ± 0.3 kcal/mole and -25.7 ± 1.4 cal/mole-deg, respectively, were evaluated for the enthalpy change and the entropy change in the present system. The effect of polar substituents on the polymerizability of aldehydes is discussed from the comparison of these values with those in the case of β-methoxypropionaldehyde.
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    Structure of chlorinated poly(vinyl chloride). III. Preparation of poly(vinyl chloride)-β,β-d2 as a model for the study of the mechanism of chlorination and of the chlorinated poly(vinyl chloride) structure (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 403-408 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method for the preparation of poly(vinyl chloride)-β,β-d2 (PVC-β,β-d 2) as a model for the investigation of the mechanism of chlorination and of the CPVC structure has been suggested. The conditions of preparation of deuterated intermediates of a multistage synthesis of vinyl chloride-β,β-d2 and of suspension-polymerized PVC-β,β-d2 have been described including the mass balance. Malonic acid was used as the starting compound. Tacticity values of a sample of PVC-β,β-d2 and its infrared and NMR spectra are presented and compared with data already published.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140212
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    Reactivity changes during polyimide formation (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 409-431 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The raactivity changes which occur in diamine monomers during polymide formation were investigated. A series of aromatic diamines were reacted with three aromatic anhydrides (including 1,4,5,8-naphthalene tetracarboxylic dianhydride) under different conditions and the products isolated and identified. There was a great range of reactivity changes depending on the conjugation between the two amino groups of the diamine monomer. For highly conjugated groups, imide formation at one group can prevent any reaction at the other, and hence polymer formation is curtailed.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140213
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    Copolymerization of styrene with vinyltriethoxysilane and vinyltriacetoxysilane (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 465-474 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Styrene was copolymerized in bulk with vinyltriethoxysilane at 80°C and vinyltriacetoxysilane at 60, 80, and 100°C with the use of benzoyl peroxide as an initiator at low conversions. Copolymer composition was determined from the silicon content and reactivity ratios were calculated by the conventional scheme of copolymerization. The low r1 value (styrene) in the styrene-vinyltriacetoxysilane system (St-VTAS) as compared to styrene-vinyltriethoxysilane (St-VTES) copolymerization may be attributed to higher reactivity of VTAS towards the polystyryl radical. Further, in the St-VTAS system, r1 tends to decrease with increasing polymerization temperature. The influence of silicon comonomer on properties of the copolymers (intrinsic viscosity, solubility, dielectric and thermal behavior) was studied.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140217
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    Metalation of unsaturated polymers by using activated organolithium compounds and the formation of graft copolymers. II (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 497-506 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polybutadiene was successfully metalated by use of tert-butyllithium activated with alkoxides of Group I metals without chain degradation. The metalated polymer was grafted with styrene and 1,3-butadiene to give novel graft copolymers of varying microstructure. This metalating system was found to be highly efficient; however, its catalyst effectiveness is less than that of organolithium-TMEDA metalation agent.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140220
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    A new type of photodegradable polymer having a pyrazine moiety in the chain (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 521-531 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photooxidative degradation of poly-2,5-distyrylpyrazine (poly-DSP) has been studied in detail. Both amorphous poly-DSP film and poly-DSP solution were photooxygenated and degraded by irradiation by sunlight in the air. The nitrile group was formed, together with carbonyl groups and hydroxyl group. The photodegradation of a pyrazine derivative to a nitrile derivative is a new reaction. Next, photodegradation behavior of polymers having a cyclobutane moiety in the main chain, poly-1,4-bis[2-(2-pyridyl)-vinyl]benzene (poly-P2VB) and polydiethyl p-phenylenediacrylate (poly-p-PDA Et), was studied. The photodegradability of these polymers decreases in the order: poly-DSP 〉 poly-P2VB ≫ poly-p-PDA Et. Further, the photodegradation behavior of various vinyl polymers containing a vinylpyrazine or vinylpyridine component and polyamides having pyrazine or pyridine ring in the main chain, was investigated. Of these, polyvinylpyrazine has the largest photodegradability.
    Additional Material: 2 Ill.
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    Studies on the photooxidation mechanism of polymers. IV. Effect of ultraviolet light (2537 Å) on solid PVC particles suspended in different liquids (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1447-1462 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of virgin PVC powder suspended in water, methanol, n-hexane, aqueous NH4OH (30 wt-%), and 0.1 wt-% iodine in methanol and also as dry powder was studied. The mechanism of photolysis of PVC powder has been investigated by using ESR spectroscopy, conductivity titration, gel-permeation chromatography (GPC), and absorption spectroscopy. Photolysis of PVC has been found to occur by a free-radical mechanism. ESR spectroscopy permits a partial identification of several different types of free radicals in PVC such as alkyl, polyenyl, and peroxy radicals. An interpretation is proposed of the mechanism of formation of conjugated polyene structures, and also a new explanation of the crosslinking mechanism, in which transfer of unpaired electrons to double bonds occurs, is suggested. It has also been found that conjugated double bonds can photosensitize free-radical formation as a result of increased ultraviolet absorption due to polyene structures.
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    High-resolution NMR studies on radiolytic reactions in polyethylene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1513-1517 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-resolution NMR spectra was obtained for linear polyethylene powder irradiated by 60Co γ-rays in vacuo or in air. For the sample irradiated in vacuo, the spectra consist of two components having different line width. The narrow component was assigned to soluble molecules and the broad one to gel. When samples are irradiated in air, their spectra show no broad component. The GPC curves obtained for the samples irradiated in air shift to high elution counts (low molecular weight) upon increase of the irradiation dose. It is concluded that oxidative degradation is the predominant reaction in the sample irradiated in air.
    Additional Material: 6 Ill.
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    1H-NMR spectra of complexes between methacrylic monomer and ethylaluminium dichloride in toluene and methylene chloride (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 237-255 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1H-NMR spectra of mixtures of a methacrylic monomer such as methacrylonitrile or methyl methacrylate and ethylaluminium dichloride at various molar ratios were measured in toluene or methylene chloride at various temperatures. It was found that only one kind of binary complex is detectable in the methacrylonitrile-ethylaluminum dichloride equimolar mixture, while in nonequimolar systems there are several kinds of binary complexes, depending on the molar ratio at low temperature in these solvents. Moreover, the chemical shifts of the protons of methacrylonitrile due to complex formation with ethylaluminum dichloride show a remarkable temperature dependence in toluene, but not in methylene chloride. This fact can be interpreted by an assumption of the formation of a ternary complex of methacrylonitrile, ethylaluminum dichloride, and aromatic donor molecules, mainly due to the dipole interaction between the nitrile group complexed with ethylaluminum dichloride and aromatic donor. The orientation of toluene molecules in the ternary complex of methacrylonitrile or methyl methacrylate is discussed.
    Additional Material: 12 Ill.
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    Chemorheology of linear polymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 265-270 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structural changes brought about by chemical reactions are reflected in the viscoelastic behavior of polymers. Viscoelastic behavior induced by such chemical reactions is called chemorheology. This phenomenon is not readily observed in linear polymers, because molecular flow by diffusion is generally much more rapid than relaxation or flow caused by chemical reaction. It has become possible, however, to treat chemorheology of linear polymers theoretically by taking such physical flow into consideration. The experimental results for linear polystyrene compared with the theoretical ones are described in this paper. Good agreement between theoretical results and experimental ones is obtained for monodisperse polystyrene with low concentration of accelerators.
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    Determination of molecular weight distribution of cellulose by conversion into tricarbanilate and fractionation (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 287-298 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two samples of cellulose (molecular weight 2.97 × 105 and 1.25 × 105) were transformed into carbanilates (CTC) which were then fractionated by the elution method at a constant composition of the acetone-water elution mixture with the column temperature gradually increasing from -30°C to 30°C, and by the GPC method in acetone and tetrahydrofuran. Tetrahydrofuran appeared to be a more suitable solvent. The molecular weights of fractions obtained by the elution fractionation were determined by the light-scattering method in tetrahydrofuran. The width of fractions was determined by the GPC method (average Mw/Mn = 1.37); the [η] values and the Mark-Houwink constants (K = 5.3 × 10-3, a = 0.84) for tetrahydrofuran at 25°C were determined. The calibration curve for the GP method was constructed by means of the fractions thus obtained; it was demonstrated that the universal calibration curve according to Benoit can also be used. It was demonstrated that the molecular weight distribution of cellulose can be conveniently determined by conversion into CTC followed either by the elution fractionation (for preparative purposes) or by fractionation by the GPC method (for analytical purposes).
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140202
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    Interaction between dyes and polyelectrolytes. I. Effect of polyelectrolytes on the reaction of methylene blue with 1-benzyl-1,4-dihydronicotinamide (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 343-351 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of polyelectrolytes on the reaction of methylene blue with 1-benzyl-1,4-dihydronicotinamide was investigated. An accelerating effect was observed on addition of sodium polystyrenesulfonate of poly(potassium p-styrenesulfonate). On the other hand, deceleration was observed on addition of potassium polyvinylsulfate. No appreciable effect was observed when sodium p-toluenesulfonate or potassium chloride was used as an electrolyte. An obvious color change was observed when methylene blue is bound to these anionic polyelectrolytes. Some correlations with spectral change of methylene blue and acceleration or deceleration effect are discussed.
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    Urea-formaldehyde resins: NMR study on base-catalyzed reaction of formaldehyde with urea in deuterium oxide (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 387-401 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-resolution nuclear magnetic resonance has been used in order to investigate the base-catalyzed reaction of formaldehyde with urea in deuterium oxide. We investigated the effects of temperature and concentration on the chemical shift of glycol species in formalin under basic condition. Assignment of all the signals appearing in the addition reaction was completed. The formation of N,N-dimethylolurea, uron, monomethyloluron, and dimethyloluron was observed for the first time, as well as the formation of monomethylolurea, N,N′-dimethylolurea, and trimethylolurea, which had been observed previously: the formation of presumptive tetramethylolurea could not be observed. The rate constants and equilibrium constant for urea, monomethylolurea, N,N′- and N,N-dimethylolurea, and trimethylolurea were estimated by analysis of the decomposition reactions of monomethylolurea and N,N′-dimethylolurea.
    Additional Material: 11 Ill.
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    Structure of poly(maleic anhydride) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1797-1807 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bulk polymerization of maleic anhydride initiated with acylperoxides, di-tert-butyl peroxide, AIBN, or pyridine proceeds with evolution of CO2. The amount of CO2 generated depends on the nature and the concentration of the initiator. With peroxide initiators, less than 5% of the polymerized maleic anhydride is decarboxylated. 1H-NMR spectra, obtained on the benzoyl peroxide-initiated polymer and its methyl ester, are consistent with the unrearranged poly(maleic anhydride) structure and rule out the polycyclopentanone structure proposed by Braun and co-workers. Base-initiated polymaleic anhydride is substantially decarboxylated, and the resulting polymer has anhydride and carboxyl groups. Elemental analyses and 1H-NMR spectra obtained on the pyridine-initiated polymer and its methyl ester refute both the cis-poly(vinylene ketoanhydride) structure suggested by Schopov and the polycylopentanone structure proposed by Braun and co-workers.
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    Polymerization of N-vinylcarbazole. II. Kinetic studies on polymerizations involving azoisobutyronitrile and benzoyl peroxide (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1819-1824 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of N-vinylcarbazole at 60°C in benzene has been initiated with azoisobutyronitrile, benzoyl peroxide, and their mixtures. The kinetics indicate that the azonitrile and the peroxide promote polymerizations of fundamentally different types. The resulting polymers have been examined by gel-permeation chromatography. The polymer produced with benzoyl peroxide contains a small amount of a high molecular weight fraction which, from the point of view of end groups, resembles the polymer made by use of the azonitrile. It is concluded that benzoyl peroxide in this system gives rise to two types of polymerization which occur simultaneously.
    Additional Material: 2 Ill.
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    Cure of unsaturated novolacs by addition polymerization (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2323-2325 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140922
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    Crystalline copolyamides of β-(4-aminophenyl)-propionic acid and caprolactam (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2407-2414 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methyl β-(4-aminophenyl)propionate was prepared and converted to a crystalline polyamide. The copolymerization of β-(4-aminophenyl)propionic acid or its methyl esters with caprolactam resulted in polyamides having wide ranges of crystallinity and thermal stability, depending on the chemical composition. Copolymers with 10, 50, 85, 90, and 95 mole-% of caproamide sequences were shown by x-ray and differential scanning calorimetry to be semicrystalline. The composition and thermal stability of the polyamides were studied by infrared spectroscopy and thermogravimetric analysis, respectively.
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    Determination of branching in polyethylene and poly(vinyl chloride) using pyrolysis gas chromatography (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2479-2495 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of polyethylenes (PE), reduced poly(vinyl chlorides), and precursor poly(vinyl chloride) (PVC) systems were studied by pyrolysis-gas chromatography (PGC) and by pyrolysis-hydrogenation-gas chromatography (PHGC). The branch content of these polymers has been interpreted on the basis of previously established literature information. Low-density PE (LDPE) was found to contain a significant number of ethyl branches. The pyrolysis results on an LAH-reduced PVC series gave significant insight on PVC microstructure. It was determined that the short-chain branches in PVC are mainly one carbon long. Some ethyl side chains and virtually no butyl branches were found in this experimental PVC series. The effect of chain branching on the pyrolysis of PVC is to increase fragmentation. The benzene/toluene ratio, along with relative amounts of benzene and naphthalene formed, may be used to indicate the relative degree of branching in this system. The application of PGC and PHGC have thus been shown to successfully extend analytical work on PE and PVC and to provide microstructural information.
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    Formation of free radicals in photoirradiated cellulose. VIII. Mechanisms (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2497-2512 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photoinduced free radicals in cellulose were studies by means of ESR spectroscopy. Plausible mechanisms have been suggested for each type of intermediate radical to account for the ESR spectra observed and for the product balances. Based on the principles of photochemistry of cellulose, coupled with the findings of the ESR spectra, it becomes evident that localization of the energy absorbed in the cellulose molecule leads to formation of free radicals in terms of chain scission, dehydrogenation, dehydroxylation, and dehydroxymethylation. Emphasis has been placed on the correlation of the mechanisms of photodegradation and the mechanisms of photoinduced graft copolymerization.
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    Vinyl polymerization. CCCXXXIX. Effect of chain length of nylon 3 on the polymerization of methyl methacrylate initiated with the system of nylon 3, copper(II) ion, and water (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2695-2702 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It was found recently that the system of nylon 3, copper(II) ion, and water could initiate a radical polymerization of methyl methacrylate(MMA). In the present paper, the effect of average chain length of the molecules of nylon 3 on the rate of polymerization of MMA was studied. The rate increased with the chain length of nylon 3. This result was explained well by the fact that the shorter nylon 3 forms a complex with copper (II) ion more easily than longer nylon 3. It was assumed that the shorter nylon 3 fills three or four coordination sites of copper(II) ion and loses the ability to initiate the polymerization. The efficiency of grafting of MMA and the degree of polymerization of MMA homopolymer were independent of the chain length of nylon 3.
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    ESR and NMR study of the γ-ray-induced postpolymerization of vinyl monomers adsorbed on zeolite (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2703-2724 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The γ-ray-induced postpolymerization of acrylonitrile and methyl methacrylate adsorbed on Linde zeolite 13X irradiated at 77°K has been studied between 303 and 343°K as a function of the amount of adsorbed monomer and of the irradiation dose. The change in the nature and the concentration of free radical with temperature and duration of the postpolymerization was followed by the ESR method, whereas the formation of polymer was monitored continuously by the decay of the 1H-NMR absorption line of the monomer under high-resolution conditions. It was found that the overall postpolymerization kinetics may be accounted for by assuming an exponential decay of radical propagation and recombination reactions with chain length. The tacticity of the polymer recovered by destroying the matrix in hydrofluoric acid was determined by 13C-NMR. The probability of isotactic addition of AN and MMA is larger than in the radical polymerization in solution owing likely to the association of adsorbed monomer molecules in pairs preforming an isotactic diad.
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    Linear polybenzyls. II. Lack of structure control in benzyl chloride polymerization (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2749-2761 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polybenzyls were prepared from benzyl chloride with different catalysts and solvents and at different temperatures. A model compound reaction for the polymerization was studied by reacting benzyl chloride with an excess amount of diphenylmethane to determine the effect of reaction conditions on substitution distribution. The degree of branching of polybenzyl samples was characterized from the infrared absorption spectra by using peaks assigned to para and ortho disubstitution products and monosubstitution units. The degree of branching so obtained correlated well with the results from the model compound reactions and with the thermal stabilities of the polymers. Anthracene unit formation was also related to the isomer content, and addition of complexing agents such as SO2 or tetranitromethane caused a reduction in branching during polymerization. An unusual glass transition behavior was observed in these polymers.
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    Rotating ring-disk electrode studies of the reaction of stable radical cations with styrene and isobutyl vinyl ether (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2763-2771 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An electroanalytical technique has been utilized in a new method for the study of reactive intermediates in polymerization reactions. A ring-disk electrode system generated persistent carbocation radicals whose stability decreased in the order: 1,3,6,8-tetraphenylpyrene (TPP), rubrene (Ru), 9,10-diphenylanthracene (DPA), and 9,10-dimethylanthracene (DMA). Radical cations from these parent compounds flowed to a collecting ring which was controlled potentiostatically to reduce unreacted cations. When styrene or isobytyl vinyl ether was added to the solution, the concentration of carbocation radicals reaching the electrode was reduced. Current collection efficiencies N were determined as a function of rotation speed ω for each monomer concentration. Plots of N-1 as ω-1 in the absence of monomer show no dependence on ω (indicative of stable intermediates), but a linear dependence is found with each concentration of monomer. This indicates a first-order dependence on radical cation concentration. The rate constants show a trend in cation reactivities which is in agreement with that obtained by other methods. This technique, however, extends the range of investigation to a much shorter time scale.
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    Solvent effects on the radiation-induced graft polymerization of styrene onto poly(isobutylene oxide) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2773-2783 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The graft polymerization of styrene onto preirradiated poly(isobutylene oxide) (PIBO) with methanol and benzene was studied. The order of grafting yield and of the number-average molecular weight of graft chains decrease in the order; undiluted styrene 〉 styrene-methanol (1:1) solution 〉 styrene-benzene (1:1) solution. A kinetic treatment to calculate rate constants from the rate of grafting and the molecular weight of the graft chain was proposed. The propagation rate constant kp was 0.2-0.3 l./mole-sec and the termination rate constant kt was 1.0-16.0 l./mole-sec. The ratio kp/kt in this heterogeneous system was larger than that in homogeneous system by a factor of about 104-105.
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    Functional polymers. II. Preparation and polymerization of methyl 5-vinylsalicylate, methyl 5-vinylacetylsalicylate, 5-vinylsalicylic acid, and 5-vinylacetylsalicylic acidThis paper is dedicated to Professor George Manecke on the occasion of his 60th birthday, with best personal wishes.Part of this work was presented at the 6th NERM Burlington, 1974, No. 165, and at the IUPAC Symposium on Modified Polymers, Their Preparation and Properties, Bratislava, 1975. For Part I of this series, see Bailey et al.1Professor M. Hartmann, University of Jena, DDR, informed us that his research group also accomplished the synthesis of methyl 5-vinylsalicylate using the same synthesis route as we describe in this paper. The synthesis in our two laboratories was carried out simultaneously and independently, and we have agreed that the results be published also simultaneously. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2725-2747 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four new derivatives of 5-vinylsalicylic acid were prepared and their homopolymerization and copolymerization with acrylic acid and methacrylic acid investigated. Methyl 5-vinylsalicylate was prepared in a six-step synthesis from methyl salicylate in an overall yield of 35%. Acetylation in the last step yielded methyl 5-vinylacetylsalicylate. Hydrolysis of methyl 5-vinylsalicylate gave 5-vinylsalicylic acid which was acetylated to 5-vinylacetylsalicylic acid (5-vinyl aspirin). The 5-vinyl-substituted salicylic acid derivatives could be readily homopolymerized and copolymerized with acrylic acid and methacrylic acid to give various compositions of copolymers. It is worth noting that even the monomers with free phenol groups could be readily polymerized with azobisisobutyronitrile as radical initiator to high molecular weight polymers without interference of the phenolic OH group.
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    Triphenylmethyl hexafluoroarsinate-initiated polymerization of 1,2-butylene oxide (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2853-2866 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of 1,2-butylene oxide initiated with triphenylmethyl hexafluoroarsinate in the -20 to +25°C temperature range with 1,2-dichloroethane as solvent is characterized by a rapid nonstationary initial stage. This is followed by a second slower stage, during which the disappearance of monomer is first-order with respect to its concentration. The conversion of monomer at the end of the first stage is related to the initial catalyst concentration but not to the initial monomer concentration. Invoking the hypothesis of an instantaneous initiation reaction, the experimental results lead to the conclusion of the existence of a unimolecular termination step. Propagation-to-termination rate constant ratios yield a propagation-termination activation energy difference of 5.9 kcal/mole. The termination step proposed is thought to involve the formation of stable macrocyclic oxonium ions. These, in turn, can reactivate the polymerization by an intramolecular reaction leading to the formation of new active centers. An energy of activation of 8.7 kcal/mole was calculated for this reactivation. GPC analyses of the reaction products recovered at the end of the first stage revealed the presence of large proportions of oligomers. Based on kinetic data, the formation of oligomers is explained by a backbiting process similar to the reactivation reaction suggested for the initiation of the second stage.
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    Grafting of styrene onto low molecular weight polymers and copolymers of butadienePaper presented at International Conference on Modified Polymers, their Preparation and Properties, Bratislava, Czechoslovakia. July 1-4, 1975. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 2875-2886 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The grafting of styrene onto low molecular weight polybutadienes and butadiene-styrene co-polymers was studied. A mathematical method was used for the design of experiments and for the determination of the optimum grafting conditions with respect to the conversion of styrene and the efficiency of grafting. The reaction parameters were temperature (65-105°C), time (2-10 hr), concentration of the initiator, polymer to monomer ratio (10/90-90/10) and dilution by solvent (toluene). The optimum grafting conditions were chosen under which 50-60 wt-% of styrene was grafted onto backbone polymer at a high conversion of the monomer. It was found that the reactions producing graft copolymer prevailed over the styrene homopolymerization when the temperatures employed were lower (65-85°C), and the reaction time (8-10 hr), backbone polymer/monomer ratio, and the dilution by solvent were higher. The efficiency, density, and degree of grafting were found to increase with the increase in the molecular weight of the backbone polymer. The efficiencies and densities of grafting onto low molecular weight polybutedienes were higher than those of grafting onto low molecular weight butadiene-styrene copolymers. Grafting efficiencies and grafting densities were in the ranges 37.8-61.6 wt % and 0.06-0.26, respectively, in the studied range of number-average molecular weights (M̄n = 2400-6000).
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    Molecular mobility of α-substituted β-propiothiolactones and their polymerizability (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 777-779 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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    Effect of nonpolar field formed by polymer ligand on the oxidation of 2,6-xylenol catalyzed by Cu complexes (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 825-832 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidative polymerization catalyzed by Cu(II)-poly(vinylpyridine) derivatives and the effect of the nonpolar field formed by the polymer ligand on the catalysis was studied in dimethyl sulfoxide (DMSO) solvent. The catalytic activity of the Cu complex increases in the following order; Cu-(styrene-vinylpyridine copolymer) (St·VP) complex 〉 Cu-partially quarternized (by benzyl chloride) poly(vinylpyridine)(BCQP) complex 〉 Cu-poly(vinylpyridine) (PVP) complex 〉 Cu-pyridine (Py) complex 〉 Cu-partially quarternized (by ethyl bromide) poly(vinylpyridine) (EBQP) complex. This order is the same as that of the reoxidation rate constant of the catalyst. Acceleration of ko process in Cu-St〉VP and Cu-BCQP systems, where the active site is in the nonpolar field formed by the polymer ligand, is explained by an increase in strength of the coordination bonds.
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    Spatially intermittent polymerization (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 869-881 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel reactor has been designed which permits the precise determination of absolute rate constants in photoinitiated free-radical vinyl polymerization. A solution of monomer and initiator flows through a dark tubular reactor past regularly spaced slots through which light shines. The alternating dark and light regions produce spatially intermittent polymerization (SIP) and make the system analogous to the well-known rotating-sector technique. However, the SIP reactor has the advantage of producing large volumes of reaction product, at low conversion, suitable for analysis of both conversion and molecular weight. This supplies the necessary data, from a single set of experiments, for the simultaneous determination of the rate constants for propagation and termination. Experimental data are reported at 25°C for methyl methacrylate which indicate that kp = 315 I./mole-sec, independent of polymer molecular weight, and kt is dependent on molecular weight especially at low molecular weight, approaching a lower value of kt = 30 × 106 I./mole-sec at a molecular weight of 106. For styrene, measurements being made only at high molecular weight, kp = 74 ± 5 and kt = 37 ± 0.3 × 106 l./mole-sec at 25°C.
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    Kinetics and mechanism of the thermal reaction between tert-butyl perbenzoate and n-alkanes: A model system for the crosslinking of polyethylene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1495-1511 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal reaction between tert-butyl perbenzoate and n-alkanes has been studied under conditions as close as possible to those during actual crosslinking of polyethylene. Product analysis allowed a description of the fate of 90-95% of the peroxide fragments. Approximately 50-60% of the substrate radicals, formed upon hydrogen abstraction, were found to combine and give crosslinks, whereas about 30% showed disproportionation, thus leading to substrate unsaturation. The two competing reactions account for 85-90% of the generated substrate radicals. The model system provides a simple and convenient method for comparing the crosslink efficiencies of peroxides; these data are reported for some commercial peroxides. In order to facilitate an extrapolation of the results in liquid alkanes towards solid polyethylene (PE), the influence of substrate viscosity and temperature on the peroxide decomposition rate, product distribution, and crosslink efficiency was studied. In n-alkanes peroxide decomposition follows first-order kinetics well, with an Arrhenius activation energy of 32.9 ± 0.5 kcal/mole. In addition, the kinetics in the model system are compared with those calculated from Rheometer (torque vs. time) measurements on the curing of unfilled PE and ethylene-propylene-dicyclopentadiene terpolymer (EPDM). Only minor differences in peroxide decomposition rate and overall activation energy were found.
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    Effects of diethylzinc in alkyllithium-initiated polymerizations (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 379-386 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In an alkyllithium-initiated polymerization of butadiene or styrene, dialkylzinc complexed with the initiator and effectively increased the initiation rate. This is particularly true with initiator of low solubility due to its very high state of aggregation. Dialkylzinc also complexes with the aggregated polymer-lithium molecules to give a lower apparent solution viscosity. In the presence of a base such as tetrahydrofuran, diethylzinc served as chain-transfer agent.
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    Poly(vinyl alcohol) hydrogels: Reinforcement of radiation-crosslinked networks by crystallization (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 441-457 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aqueous poly(vinyl alcohol) solutions were crosslinked via electron-beam irradiation to form transparent hydrogels of varying crosslinking densities. Typical crosslinked hydrogels with Mc between 3500 and 8000 were weak, easily shattered, nonextensible materials with very low tensile moduli (up to 70 psi) and tensile strengths at break (less than 10 psi). Reinforcement by induction of partial crystallization was accomplished by a two-stage drying process, consisting of a slow dehydration stage at room temperature and an annealing stage at elevated temperatures, which was mainly responsible for the introduction of the crystallites. The swollen hydrogels after the annealing process had crystallinities widely varying between 30 and 65% and polymer volume fractions between 30 and 60%, depending on the temperature-time history of the specimen. These materials showed greatly improved mechanical properties (modulus, ultimate tensile strength, tear strength), as compared to the uncrystallized hydrogels.
    Additional Material: 16 Ill.
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    Free-radical polymerization of vinylferrocene. II. Spectroscopic and physical properties (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 475-488 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The spectroscopic and physical properties of poly(vinylferrocene) prepared by free-radical polymerization in benzene are discussed. The results obtained in these studies are in accord with the kinetic analysis of the polymerization reactions in benzene. ESR spectroscopy shows that the polymer is paramagnetic and contains a species which is identified by Mössbauer spectroscopy as an ionically bound complex of Fe(III) in a high spin (3d5) configuration. The concentration of this species is shown to be dependent upon kinetic parameters. Magnetic susceptibility measurements show that the polymer does not contain any oxidized ferromagnetic impurities. Infrared spectroscopy indicates that the polymer contains vinylidene groups. The presence of these groups is explained by chain transfer to monomer followed by reinitiation. Ultraviolet spectroscopy also suggests the presence of unsaturation in the polymer. Gel-permeation chromatography indicates that poly(vinylferrocene) is branched even at low conversions. The effect of transfer reactions and the intramolecular electron transfer termination of the chain radical on the structure of poly(vinylferrocene) is discussed. The glass transition temperature and thermal stability of the polymer are also examined.
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    The paracrystalline state of synthetic polymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 519-519 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140224
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    Eine quantitative, UV-photometrische bestimmung von Endgruppen in polystyrolenHerrn Prof. Dr. H. Mark mit allen guten Wünschen zum 80. Geburtstag gewidmet. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 609-615 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Styrene was polymerized in bulk for 45 min at 70°C under a nitrogen atmosphere to a conversion of 6.16 weight-percent with an aliphatic azo compound, which contained four p-methoxyphenyl groups per molecule. The polystyrene could be purified easily by column chromatography and was then free of initiator and its decomposing products. It was separated into ten fractions by fractional precipitation (toluene/methanol), and the molecular weights of the polystyrenes were determined osmotically. The ultraviolet absorptions of the polystyrene solutions in dioxane were optically constant and followed the Bouguer-Lambert-Beer law. This made it possible to determine the number of absorbing groups per polystyrene molecule, which were constant with a value of 2. Polystyrenes with a number average molecular weight to 106 should be determinable in the same way.
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    Polymerization of coordinated monomers. XI. Structure and reactivity of the ternary molecular complex composed of stannic chloride, methyl methacrylate, and styrene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 627-654 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The time-averaged orientation of styrene in the ternary molecular complex composed of stannic chloride, methyl methacrylate, and styrene was determined by use of the chemical shift changes of the protons in the methyl methacrylate on the ternary molecular complex formation. The observed chemical shift change for each of the protons in the methyl methacrylate is expressed by the weighted average of the shifts due to the anisotropic shielding of the benzene ring of styrene for conformations I and II, using the common statistical weight. Conformations I and II correspond to the cis and trans rotational isomers, respectively, of methyl methacrylate with respect to the rotation of the methoxymethyl group around the carbonyl carbon-ether oxygen bond. Extended Hückel calculations were made on the methyl methacrylate monomer coordinated to stannic chloride and styrene monomer as well as the growing radicals corresponding to the monomers. The energy levels of the frontier orbitals of the species were determined by use of the ionization potentials, the absorption maxima, and the results of the extended Hückel calculations. The high reactivity of the ternary molecular complex is discussed in terms of the interactions between the frontier orbitals of the styrene and those of the coordinated methyl methacrylate.
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    Cationic polymerization of vinyl monomers initiated by phosphorus compounds containing halogens (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 685-692 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of vinyl monomers having large negative e values in the presence of phosphorus compounds containing halogens was studied in order to examine the cationic initiation ability of phosphorus compounds. N-Vinylcarbazole was effectively polymerized by phosphorus compounds such as PCI3, PBr3, PCI2C6H5, PCI(C6H5)2, POCI3, and POCI2C6H5 even in benzene. The initiation ability of phosphorus compounds decreased in the order; PCI2 ≃ PBr3 〉 PCI2C6H5 〉 PCI(C6H5)2, and also POCI3 〉 POCI265. On the other hand, PCI3 and PBr3, which were less effective than POCI3, showed initiation ability for the polymerizations of styrene and α-methylstyrene in nitrobenzene as a solvent. The results of the copolymerization of styrene with methyl methacrylate by PCI3 in nitrobenzene, the result of solvent dielectric constant effect, and the effect of additives such as water, tert-butyl chloride, triethylamine, and hydroquinone, indicate the polymerization of styrene by PCI3 to proceed by a cationic mechanism.
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    Determination of coisotacticities of some alternating styrene-acrylic copolymers by NMR spectra (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 57-71 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Coisotacticities σ for some alternating copolymers were determined through the analyses of their CH3O, CH3 and CH2 proton NMR spectra; styrene-methyl methacrylate (σ = 0.56), styrene-methyl acrylate (σ = 0.53), styrene-methyl α-chloroacrylate (σ = 0.69), styrene-methacrylonitrile (σ = 0.19), styrene-methacrylamide (σ = 0.16), α-methylstyrene-methyl methacrylate (σ = 0.21), and α-methylstyrene-methyl acrylate (σ = 0.53) were studied. It was found that a terminal model or Bernoullian trial prevails in these complexed copolymerizations with diethylaluminum chloride. The influence of monomer structure on σ values is discussed.
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    Emulsion copolymerization behavior of α-methylstyrene with methacrylonitrile (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 105-111 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The emulsion copolymerization behavior of α-methylstyrene with methacrylonitrile is described. The effects of polymerization temperature, potassium persulfate initiator concentration, sodium lauryl sulfate emulsifier concentration on copolymer yield, molecular weight, and rate of copolymerization are described. The copolymer was found to have an azeotropic composition at 43 mole-% AMS. Reactivity ratios were determined to be 0.06 and 0.28 for AMS and MAN, respectively.
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    Poly(vinyl chloride-g-butyl rubber) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 153-157 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of poly(vinyl chloride-g-butyl rubber) and some of its physical properties are described. The key to the synthesis involves copolymerization initiation of an isobutylene-isoprene charge by a PVC/Et2AlCl initiator system with 1,2-dichloroethane as solvent. The graft is a thermoplastic; cast films are flexible and optically clear. Proof of grafting is the crosslinking with S2Cl2 of the pentane-extracted product in THF solution. Crosslinking the butyl rubber moiety in the graft reduces overall stress properties.
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    Effect of gegen ion in cationic polymerization and copolymerization of trioxane (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 129-142 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: p-Chlorophenyldiazonium hexafluorophosphate has been reported to be a superior catalyst for cationic polymerization and copolymerization of trioxane as compared to boron trifluoride dibutyl etherate (BF3·Bu2O)1. In the present investigation the effect of anions derived from elements in Group VA, AsF6- and SbF6-, has been ascertained. It has been concluded that p-chlorophenyldiazonium hexafluoroarsenate is also a superior catalyst to boron trifluoride dibutyletherate (BF3·Bu2O), while p-chlorophenyl-diazonium hexafluoroantimonate is inferior.Copolymers with the highest polymer yield (〉95%) and molecular weight (intrinsic viscosity = 4 to 5) were obtained with Simple dependences on catalyst concentration have been observed to hold for a wide catalyst concentration range ([M]/[C]) = (1 to 20) × 105: \documentclass{article}\pagestyle{empty}\begin{document}$ \begin{array}{*{20}c} {{\rm polymer yield}} & \prop & {\left[ {{\rm catalyst}} \right]^0 } \\ {{\rm molecular weight}} & \prop & {\left[ {{\rm catalyst}} \right]^{ - 0.5} } \\ {\frac{{\left[ {{\rm chain transfer}} \right]}}{{{\rm catalyst}}}} & \prop & {\left[ {{\rm catalyst}} \right]^{ - 0.5} } \\ \end{array} $\end{document} For the same relationships hold. However, the polymer yield (75%) and molecular weights (intrinsic viscosity ≃1) are considerably lower while the extent of chain transfer is higher. Furthermore, the polymerization proceeds with explosive violence.The quantitative aspects resulting from polymerization, for the most part, can be interpreted in terms of the extent of dissociation of the propagating ions.
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    Photocatalyzed polymerization of epichlorohydrin (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1547-1548 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140621
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    Effect of a polymer ligand on the complexation kinetics of copper(II)-polyethyleneimine (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1557-1560 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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    Preparation and properties of polyamides and polymides containing bibenzyl, stilbene, and tolan structures (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1599-1607 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyisophthalamides and polyterephthalamides were prepared by the solution polycondensation of the corresponding diacyl chlorides with 4,4′-diaminobibenzyl, trans-4,4′-diaminostilbene, and 4,4′-diaminotolan in N,N-dimethylacetamide (DMAc). Polypyromellitimides were synthesized in two steps by the ring-opening polyaddition of pyromellitic dianhydride with the aromatic diamines in DMAc, followed by thermal cyclodehydration. The amorphous polyisophthalamides were soluble in some amide solvents containing lithium chloride, while the polyterephthalamides having fair degree of crystallinity were insoluble in these solvents. The thermal stability of these aromatic polymers decreased in the order of the tolan-containing polymers 〉 the stilbene-containing polymers 〉 the bibenzyl-containing polymers, both in air and under nitrogen.
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    Applications of ESCA to polymer chemistry. X. Core and valence energy levels of a series of polyacrylates (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1671-1700 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The core and valence levels of a series of poly(alkyl acrylates) have been studied by ESCA. From an analysis of the individual component peaks for the C1s and O1s core levels and from comparison of relative area ratios it is shown that ESCA may be applied to the study of surface compositions. The evidence presented strongly suggests that on the ESCA depth-profiling scale the technique statistically sample the repeat units with no evidence for preferential orientation of side chains at the surface. For some samples, ESCA provides evidence for a degree of surface oxidation and hydrocarbon contamination. The valence energy levels are shown to be characteristic of the polymer system. The measured absolute and relative binding energies of the core levels have been compared with model calculations using the charge-potential model in the CNDO/2 SCF MO formalism.
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    Applications of ESCA to polymer chemistry. XI. Core and valence energy levels of a series of polymethacrylates (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1701-1713 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The core and valence energy levels of a series of poly(alkyl methacrylates) have been studied by ESCA. Surface compositions have been determined both from a comparison of area ratios for the O1s and C1s core levels and from the relative areas for the individual component peaks for these levels. The evidence presented suggests that on the ESCA depth-profiling scale the technique statistically samples the repeat unit with little or no evidence for preferential orientation of the alkyl side chain at the surface. Little evidence was found for either surface oxidation or hydrocarbon contamination at the surface of the samples studied. The valence energy levels are shown to be characteristic of the polymer system.
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    Study of radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. VII. Effect of pretreatment temperature of silica gel on styrene-silica gel system (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1743-1751 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To investigate the reaction mechanism of radiation-induced polymerization of styrene adsorbed on silica gel, the effect of pretreatment temperature of silica gel was studied. Preheating of silica gel was carried out at 200, 500, and 800°C. The number of silanol groups of silica gel surface decreased as preheating temperature increased. The rate of polymerization on the silica gel preheated at 500°C was faster than that at 200°C, but the polymerization rate on the silica gel preheated at 800°C was the lowest. These results suggest that rate of polymerization on the silica gel is affected by the conditions of silica gel surface such as the number of silanol groups and the pore size. At the same monomer conversion, percent grafting decreased as preheating temperature of silica gel increased. The GPC spectra of both graft polymers and homopolymers have two peaks at all preheating temperatures. The monomer conversion of low molecular weight peaks of graft polymers decreased as preheating temperature of silica gel increased. This result suggests that there is a probability that the grafting sites of low molecular weight peaks of graft polymers somehow interact with silanol groups.
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    Determination of interaction parameter χ1, for poly(vinyl alcohol) and water in gels crosslinked from solutions (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 459-464 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Flory interaction parameter χ1 of poly(vinyl alcohol)-water systems has been estimated as a function of temperature and volume fraction of PVA, the polymer having been crosslinked from solutions of the same in water. Values are reported for temperatures between 0°C and 90°C and polymer volume fractions between 0.03 and 0.12.
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    Syntheses of polymerizable phenol derivatives having a carbonyl-containing group as a ring substituent (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 511-514 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140222
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    Photopolymerization of methyl methacrylate and other vinyl monomers with the use of N-bromosuccinimide as photoinitiator (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 993-1004 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of MMA was done in the presence of visible light (440 nm) with the use of N-bromosuccinimide (NBS) as the photoinitiator. The initiator exponent and intensity exponent were 0.5, and the monomer exponent was found to be unity. The polymerization was inhibited in the presence of hydroquinone. The average kp2/kt for this photopolymerization system was found to be 0.296 × 10-2 and the activation energy of photopolymerization was 4.67 kcal/mole. Kinetic and other evidence indicate that the overall polymerization takes place by a radical mechanism. With NBS as the photoinitiator, the order of polymerizability at 40°C was MMA, EMA ≫ MA ≃ VA, and styrene could not be polymerized under similar conditions.
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    Radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. VI. Temperature dependence and effects of additives on methyl methacrylate-silica gel system (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1031-1041 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To elucidate the reaction mechanism of radiation-induced polymerization of methyl methacrylate adsorbed on silica gel, the temperature dependence and effects of acetone and pyridine were investigated. It was found that even at -78°C the polymerization rate was quite fast. The amounts of high molecular weight GPC peaks of both graft polymers and homopolymers increased with increasing irradiation temperature. The activation energy of the adsorbed state polymerization was low compared with that of bulk polymerization. The low molecular weight peaks of homopolymers decreased with acetone addition but were almost unaffected by pyridine. The low molecular weight peaks of homopolymers were thus polymerized by an anionic mechanism. In the methyl methacrylate-silica gel system both radical and anionic polymerization take place at the same time in formation of graft polymers and homopolymers. A reaction mechanism for the methyl methacrylate-silica gel system was proposed based on the results obtained to date.
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    Glass transitions of polyolefins by inverse gas chromatographyPaper presented in part at the 56th Canadian Chemical Conference, Montreal, 1973. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1073-1081 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The glass transition temperatures of polypropylene, poly-1-butene, polyisobutylene, and an ethylene-propylene (EP) copolymer have been determined by inverse gas chromatography. The results are consistent with those determined by other procedures. When applied to low-, medium- and high-density polyethylene, values of -35, -25, and -18°C, respectively, were obtained. Because of the fact that the chromatographic technique involves essentially a sensitive detection of free volume in a polymer, it is suggested that these values represent Tg if it is defined as an iso-free volume state of the amorphous phase of the polyethylene.
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    Cyclopolymerization. V. Monomer design for the synthesis of highly cyclized polymer from unsymmetrical unconjugated dienes: Synthesis and polymerization of N-methyl-N-allylmethacrylamide (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1107-1115 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-Methyl-N-allylmethacrylamide (MAMA) was synthesized and polymerized with radical initiators, and the structure of poly-MAMA was studied, in order to establish the concept that difunctional monomers having monofunctional counterparts which do not polymerize are likely to give rise to highly cyclized polymer, if the cyclized polymer is in a lower free-energy level than the monomer. The cyclopolymerizability of MAMA was considerably higher than that of N-allylmethacrylamide, which was previously reported, and its monofunctional counterpart can be polymerized. The extent of cyclization of poly-MAMA was about 93%, even in the polymer obtained by bulk polymerization. The repeating units of poly-MAMA consist mainly of five-membered rings; six-membered rings and pendent methacryl groups were detected in addition as minor repeating components. The monofunctional counterparts of MAMA, i.e., N-methyl-N-n-propylmethacrylamide (MPMA) and N-methyl-N-allylisobutyramide (MAIA), were also synthesized. Neither MPMA nor MAIA showed any tendency toward polymerization under the same experimental conditions as used for MAMA. The results thus obtained all support the concept mentioned above.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140508
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    Electropolymerization of aminophthalic acids. II. Polymerization of 4-(4′-aminobenzamido)-, 4-(2′-aminobenzoyl)-, and 4-(3′-aminobenzoyl) phthalic acid (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1151-1156 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electrochemical polymerization of the amino phthalic acid series has been extended to the following derivatives: 4-(4′-aminobenzamido), 4-(2′-aminobenzoyl), and 4-(3′-aminobenzoyl)phthalic acid. Reactions were performed in both dimethylacetamide and ethanol. Both systems produced a film deposit at the anode which was identified as the amide acid of the starting material. Conversion by heat to the imide produced a brittle coating. Inherent viscosity measurements indicate that only low molecular weight material was formed.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140512
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  • 286
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    Morphology of organosilicon ladder polymers (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1205-1212 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The morphology of organosilicon ladder polymers was studied by various methods, including x-ray techniques, diffraction of monochromatic polarized light, and electron microscopy. The morphology is discussed as a function of the chemical composition, the molecular weight, and the method of preparation.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140518
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    Effect of pH on radical polymerization of butadiene 1-carboxylic acid in aqueous solutions (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1195-1203 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical polymerization of butadiene 1-carboxylic acid (Bu-1-Acid) was carried out in aqueous solutions at 50°C with ammonium persulfate (APS) as an initiator. Kinetic studies led to the rate equation, Rp = k[APS]1/2 [Bu-1-Acid]1 at pH 6.8. The overall activation energy for the polymerization was 16.0 kcal/mole. The polymerization rate Rp of Bu-1-Acid decreased with an increase of pH in the range 2.4-6.8 and increased with an increase of pH in the range 6.8-8.4. Moreover, in the pH range 8.4-13, the rate of polymerization was not affected by the pH of the system. In copolymerization with acrylonitrile, the trends of changes in the monomer reactivity ratios r1, r2 and Q-e values caused by changes in pH were similar to trends found in homopolymerization described above. In addition, it was observed that the resultant polymer was extended in alkaline solution and contracted in acidic solution.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140517
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    Acceleration effect of poly(vinylpyrrolidone) on williamson reaction. II. Studies on the dissociation of sodium phenoxide in the presence of poly(vinylpyrrolidone)For the previous paper in this series, see Yamazaki et al.1 (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1229-1234 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In connection with the accelerating effect of poly(N-vinylpyrrolidone) (PVP) on a Williamson reaction, PhONa + NC4H9Br → PhO-(n-C4H9) + NaBr, the ionic dissociation of sodium phenoxide (PhONa) was studied by means of conductance measurements and ultraviolet spectroscopy. Results suggest that the degree of dissociation of PhONa increased with the amount of PVP as well as N-methylpyrrolidone (NMP), the monomeric analog, the effect of PVP being much larger than that of NMP at the same concentration. It is assumed that free phenolate anion produced by solvation of sodium cation with NMP or the pyrrolidone residues of PVP plays an important role in the acceleration of the reaction and that the higher reaction rates in PVP solution are due to the greater dissociation of PhONa.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140521
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    Chemical behavior of optically active poly[thio 1-(N,N-disubstituted aminomethyl) ethylenes] in CuCl2-methanol mixtures: Induced optical activity of bound Cu(II) (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1257-1265 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (+)-Poly[thio 1-(N-sec-butyl-N-methylaminomethyl) ethylene] (I) and (-)-poly[thio 1-(N-methyl-N-(1-phenylethyl)aminomethyl) ethylene] (II) are soluble in methanol or in a 10/90 dioxane-methanol mixture in the presence of CuCl2. This salting-in effect results from interactions between macromolecules and this salt. With a large excess of salt (molar ratio 〉 8) a precipitate is obtained whose composition is close to a CuCl2:monomer unit ratio of unity. Ultraviolet, optical rotatory dispersion (ORD) and circular dichroism (CD) spectra in solution are described. The three extrinsic Cotton effects observed between 300 and 800 nm are assigned to charge transfer and d-d electronic transitions of Cu(II) complexed with the macromolecules. In the same solvent system, Cu(II) shows similar induced optical activity in the presence of a nonaminated homolog, (+)-poly(propylene sulfide) taken as a model of the chains of I and II. No extrinsic Cotton effects are observed in the presence of an optically active tertiary amine without the thioether sulfur atom, (+)-N-sec-butyl-N-methyl-N-(oxirane-2-ylmethyl)amine. It is concluded that Cu(II) gives rise to charge-transfer complexes with sulfur atoms, while tertiary amine groups are probably protonated in this particular medium.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140525
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    Syntheses of polymerizable hydroquinone derivatives (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1235-1240 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several polymerizable hydroquinone derivatives were prepared by the Williamson synthesis. Thus, hydroquinone mono(p-vinylbenzyl) ether (III-1), hydroquinone methyl p-vinylbenzyl ether (III-4), and hydroquinone benzyl p-vinylbenzyl ether (III-5), tert-butylhydroquinone mono(p-vinylbenzyl) ether (III-2), and 2,5-di-tert-butylhydroquinone mono(p-vinylbenzyl) ether (III-3) were synthesized by the reactions of p-chloromethylstyrene with the corresponding hydroquinone derivatives in alcoholic potassium hydroxide or with their potassium salts in dipolar aprotic solvents. All monomers were found to polymerize by free-radical initiation except III-3, which required a cationic initiator.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140522
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    Effects of stannic chloride on copolymerization of benzalacetophenone or benzalacetone with methyl methacrylate and styrene (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1287-1292 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140529
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    Polymerization of acetaldehyde. I. A new polymerization process with tetraisopropyl titanate catalyst (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1297-1299 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140531
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    Solution properties of phosphonitrilic fluoroelastomersPaper was presented, in part, at the Technology Assessment and Planning Conference-Phosphazene and Phosphazene High Polymers, Army Materials and Mechanics Research Center, Watertown, Mass., May 20-22, 1975. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1379-1395 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of phosphonitrilic fluoroelastomers which have excellent solvent resistance and low temperature flexibility, and which perform well under a broad range of service conditions, have been developed. The solution properties of one of these polymers were studied more extensively in order to develop suitable quality control procedures and to gain a better understanding of the polymer structure. Solvents for these procedures were established, fractionation procedures were developed, and intrinsic viscosity, osmotic pressure, and light-scattering measurements were conducted. We found this polymer to have a very broad molecular weight distribution. And, although fractionation by molecular weight was effected, the fractions retained a broad molecular weight distribution. Our data do not indicate significant branching for this polymer. As a result of our studies, we have theorized that a supermolecular structure may be present in this polymer.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140607
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    Studies on the photooxidation mechanism of polymers. V. Oxidation of polybutadienes by singlet oxygen from microwave discharge and in dye-photosensitized reactionsPresented in part at International Symposium on Ultraviolet Light-Induced Reactions in Polymers, American Chemical Society, Philadelphia, April 6-11, 1975. (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1463-1473 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The singlet oxygen oxidation of cis- and trans- 1,4-polybutadienes was studied by using singlet oxygen generated in a microwave generator and in dye-photosensitized reactions of these polymers in the solid state and in solution. It was shown that the reactions of singlet oxygen result in formation of hydroperoxide groups, whereas ultraviolet oxidation by molecular oxygen in addition leads to formation of carbonyl groups. During dye-photosensitized oxidation of polydienes in benzene solution, a very rapid decrease in the molecular weight was observed.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140613
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    Stereoregularity of poly(2-vinylpyridine) determined by 1H-NMR and 13C-NMR spectroscopy (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1475-1484 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to determine the stereoregularity of poly(2-vinylpyridine), 2-vinylpyridine-β,β-d2 was synthesized. The 1H-NMR spectra of the deuterated polymer in D2SO4 and o-dichlorobenzene solutions showed three peaks, which were assigned to triad tacticities. Since the absorptions of heterotactic and syndiotactic triads of methine protons overlap those of methylene protons in nondeuterated polymers, only isotactic triad intensities can be obtained from the 1H-NMR spectra of nondeuterated poly(2-vinylpyridine). The 13C-NMR spectra of poly(2-vinylpyridine) were obtained in methanol and sulfuric acid solutions. In methanol solution the absorption was split into three groups, which cannot be explained by triads, and in sulfuric acid solution several peaks were observed. These splittings may be due to pentad tacticity. The results show that poly(2-vinylpyridine) obtained by radical polymerization is an atactic polymer.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140614
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    Polyimidines, a new class of polymers. I. Phenylated polypyromellitimidines (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1485-1493 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Model compounds and polymers containing the imidine functional group have been synthesized from diphenylphthalide and tetraphenylpyromellitide by condensation with mono- and diamines. The diamine monomers included: 1,6-diaminohexane, p-phenylenediamine, and 4,4′-diaminodiphenyl ether. Reactions were run either in biphenyl or with no solvent at 250-300°C to yield up to 57% product with molecular weights up to approximately 16,000 and inherent viscosities to 0.15. All polymers were soluble in chloroform and dimethylformamide and showed thermal stabilities by TGA to range from 225°C (for aliphatic backbones) to 400°C (for aromatic systems).
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140615
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    Polyimidines, a new class of polymers. II. Polyhexamethylenetetraphenyldithiopyromellitimidine (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1519-1526 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyimidines have been shown to be soluble, thermally stable polymers. In searching for an alternate synthetic method the thio analog of this system has been discovered. The brightly colored (red-orange) perthio derivatives of 3,3-diphenylphthalide and 3,3,5,5-tetraphenyipyromellitide were synthesized from their oxo analogs with P2S5. The model compound thioimidines were synthesized by reacting 3,3-diphenyldithiophthalide with aniline and with 1,6-hexane diamine and by reacting 3,3,5,5-tetraphenyltetrathiopyromellitide with aniline and n-hexylamine. The polymerization of tetraphenyltetrathiopyromellitide occurred readily with 1,6-hexanediamine in boiling carbon tetrachloride with complete cyclization. This reaction gave an 80% yield with inherent viscosities up to 0.89 and molecular weights up to approximately 11,000. Thermogravimetric analysis showed a 2% weight loss at 200°C and 10% weight loss at 300°C with rapid decomposition above 300°C. Although the polythioimidine was less thermally stable than its oxo analog, it was much more soluble in common solvents (aromatic and chlorinated aliphatic hydrocarbons) and more readily synthesized in higher yield.
    Additional Material: 1 Ill.
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    ESR study of the macroradicals produced in polycarbonate by thermal decomposition of benzoyl peroxide at high pressure (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1549-1551 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140622
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    Effect of surface swelling on diffusion in polymers. I. Infrared spectroscopy (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1581-1597 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of stress transfer-limited swelling in the surface region on the hydroxylation of styrene-butadiene-styrene block copolymers in the bulk state was investigated. Films of the copolymer were allowed to react with peracetic acid to effect epoxidation and simultaneously with acetic acid and water to cleave the epoxy rings. By infrared spectroscopy it was observed that the hydroxyl content of the films decreased with increasing film thickness and the epoxy content increased commensurately. This was attributed to the presence of a lag between the advancing diffusion fronts for the epoxide groups and for the cleavage agents. This lag increases with increasing thickness due to the presence of stress-transfer mechanisms which act to reduce the degree of swelling in the surface region and which are more effective in thicker films. The hydroxyl content increased exponentially with time, giving rise to the observation of significant induction time before there was any infrared evidence of hydroxyl formation. This resulted from the relief of part of the compressive stress in the surface region by the reaction process, which in turn increased the permeation rate of peracid.
    Additional Material: 11 Ill.
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    Aromatic polyethers, polysulfones, and polyketones as laminating resins. VIII. Aryl disulfide units as crosslinking agentsFor Part VII, see Chang and Marvel.1 (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1637-1644 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxidation of 1,4-phenylenedimercaptan has given a cyclic trimeric disulfide. Oxidation of 1,3-phenylenedimercaptan has yielded a similar product. These monomers have been incorporated in the chains of aromatic polyether, sulfone, ketone polymers and serve as crosslinking sites on heating these polymers.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1976.170140707
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