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  • 1980-1984  (15,115)
  • Polymer and Materials Science  (15,115)
  • 301
    Electronic Resource
    Electronic Resource
    Macromonomers - a new class of polymeric intermediates in macromolecular synthesis. I - synthesis and characterization (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 8 (1984), S. 3-15 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ionic methods meant to fit a linear macromolecule with an end-standing polymerizable unsaturation are reviewed in this paper. The versatility of these methods and their ability to yield species of molecular weight chosen at will and of low polydipersity are of great interest in this matter. A large number of well-defined macromonomers, covering the molecular weight range of interest (103 to 104), have been obtained ionically. An adequate characterization of the species obtained is required to establish whether the functionalization reaction is reliable and quantitative and whether the molecular weights obtained are in good agreement with the values expected.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.020081984102
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  • 302
    Electronic Resource
    Electronic Resource
    Structural and physical modification of thermotropic liquid crystalline polymers (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 8 (1984), S. 47-61 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure and properties of thermotropic liquid crystalline polymers with side mesogenic groups are discussed. The regulation of physical and physico-chemical properties of such polymers is shown to be achieved both by the structure modification of macromolecules and by use of an electric field.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.020081984105
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  • 303
    Electronic Resource
    Electronic Resource
    Physicochemical aspects of plastic flow (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 8 (1984), S. 109-117 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the present paper are given the results of studying the processes of polymerization, polycondensation and polyaddition in solids. The processes of polymerization under high pressure and shear deformation have been shown to proceed with much larger rates than the similar processes in a liquid phase. It has been found that in a solid state the reactions do not proceed in the directions to be expected knowing the laws of the classical organic chemistry. While realizing shear deformation in solids at high pressure we have discovered superhigh molecular mobility of particles. Uniaxial deformation of polymers and polymer mixtures leads to the formation of oriented fibers while in multi-stressed state polymer is converted into powder. The results obtained during the formation of powders by elastic-deformation method have been discussed.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.020081984110
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  • 304
    Electronic Resource
    Electronic Resource
    Synthesis of macromolecular antioxidants by reaction of aromatic amines with epoxidized polyisoprenes, 2.Part 1: cf.1. Kinetics and mechanism of model reactions (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 19-25 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Kinetic and thermodynamic parameters were determined for the reaction of the unsymmetrical oxiranes 3,4-epoxy-methylheptane (1) and 1,2-epoxy-3-ethyl-2-methylpentane (4) with aniline in o-dichlorobenzene. A kinetic scheme involving two elementary reactions agrees well with the experimental results obtained for the phenol catalysed reactions. The thermodynamic parameters, especially the entropy, lead to the proposal of a concerted transfer mechanism allowing for the observed normal and abnormal addition reactions.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850103
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  • 305
    Electronic Resource
    Electronic Resource
    Untersuchungen zur klärung der sensibiliserten photodegradation von polystyrol in lösungen, 1. Experimentelle befunde zum kettenabbauZ. T. ausgeführt im Rahmen des Forschungsbereiches MR 1.9-1.4.3 der Polnischen Akademic der Wissenschaften. (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 75-80 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polystyrene (mass average molar mass M̄ = 609700 g/mol; molecular non-uniformity M̄/M̄ - 1 = 0,55) solutions in 8 different solvents were irradiated by light of a mercury lamp (wavelength λ ≥ 270 nm). The rate of photodegradation of the polymer (as determiened from ΔM̄w measurements by light scattering) is strongly solvent-dependent and only slightly dependent on the O2 concentration in the irradiated solutions. An attempt to interpret this „sensibilized“ photodegradation will be given in the second part of this series.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850108
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  • 306
    Electronic Resource
    Electronic Resource
    Initiation mechanism of free-radical polymerization of methyl methacrylate by p-substituted N, N-dimethylanilines (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 81-89 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In order to investigate the initiation mechanism of the polymerization of MMA by N, N-dimethylaniline (DMA), p-substituted DMA's were prepared and used for a kinetic study. Electron donating groups increase and electron withdrawing substituents decrease the over-all rate of polymerization. Moreover, different kinds of amines were examined as initiators. The results were related with the Hammett equation and the ionization potential of the amines. The solvent effect and the composition of the initiator complex were investigated. From these results, it is concluded that the initiating species is a 1:1 electron transfer complex of DMA with the monomer methyl methacrylate.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850109
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  • 307
    Electronic Resource
    Electronic Resource
    Oligomères amphiphiles obtenus par voie radicalaire, 3.Partie 2: cf.4. Simulation et contrôle de la synthèse d'oligomères de i'acide acrylique et de i'acrylamide à extrémité thio (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 113-127 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The synthesis of amphiphilic oligomers through radical initiated polymerization of hydrophilic monomers in the presence of long hydrocarbon chain thiols as transfer agents was simulated using a model based on a kinetic scheme similar to that proposed by Ikada. Taking into account the solvent as a secondary transfer agent, the weight fractions of different oligomer molecules and the average degrees of polymerization versus conversion were determined as a function of the mole ratio [thiol]/[monomer] and the solvent transfer constant. A relatively good agreement was found between the theoretical and the experimental values for acrylic acid (AA) and acrylamide (Am) oligomerizations. Oligomers terminated by the solvent could complete with thiol-terminated oligomers. It is interesting that by modifying the simulation model, it is possible to estimate the amount of thiol necessary to keep the composition of the reactant mixture constant during synthesis, thereby eliminating the drift in the oligomer composition at high conversion.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850112
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  • 308
    Electronic Resource
    Electronic Resource
    Thermodynamical description of deformation phenomena in rubbersDedicated to Prof. H.-J. Cantow on the occasion of his 60th birthday (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 193-203 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A fundamental thermodynamical equation is presented for a Gaussian network in an analytically closed form (Gibbs function) for modified and extended network models in a parametric form. With this equation a complete description of the deformation phenomena in rubbers can be made, embracing strain-dependent effects, related to short-range properties like thermal expansion, rotational isomerism and rotatory oscillation degrees of freedom.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850117
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  • 309
    Electronic Resource
    Electronic Resource
    Polymers containing enzymatically degradable bonds, 9. Chymotrypsm catalyzed hydrolysis of a p-nitroanilide drug model, p bound via oligopeptides onto poly(vinylpyrrolidone-co-maleic anhydride)Part 8: cf. 33. (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 231-237 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Copolymers of 1-vinyl-2-pyrrolidone with maleic anhydride which contain oligopeptide sidechains with l-phenylalanine p-nitroanilide (Phe-NAp) end groups were synthesized. The chymotrypsin catalyzed hydrolysis of these polymers was studied. The rate of p-nitroaniline release was found to depend on the structure of the oligopeptied sequences: —Gly—Gly—Val—Phe—NAp 〉 —Gly—Val—Phe—NAp 〉 —Gly—Gly—Phe—NAp. From a comparison with similar substrates based on poly[N-(2-hydroxypropyl)methacrylamide] the influence of the structure of the polymeric backbone on the rate of cleavage of bonds at the ends of oligopeptide side-chains was estimated.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850201
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  • 310
    Electronic Resource
    Electronic Resource
    Molecular weight distribution studies, 4Part 3: cf. 8. Kinetics of the gamma-ray induced free radical polymerization of vinyl acetate at low temperatures (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 317-328 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the gamma-radiation initiated free radical polymerization of vinyl acetate were studied in bulk over a temperature range of -60°C to 0°C. Four radiation dose rates of 0,83, 0,33, 0,26, and 0,079 Mrad were used. The overall rate of polymerization was found to vary with the 0,46 to 0,53 power of the radiation intensity, indicating a free-radical polymerization mechanism. The overall activation energy was found to tie between 16 and 18 kj/mol. The values of ktrm/kp and (ktc + ktd)kp2 were evaluated from the overall polymerization rates and the number-average molecular weights. The values of the radiation chemical yield GVAC were found to lie between 2,4 and 4,1.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850208
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  • 311
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    Polymer synthesis based on 2-(hydroxyphenyl)-2-oxazolinesDedicated to Professor Dr.O. Wichterle on his 70th birthday (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 441-451 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2-(Hydroxyphenyl)-2oxazolines(p- and n-isomers 1a and 1b) were used for the synthesis of various polymers. Cationic polymerization of 2-methyl-2-oxazoline initiated with the N-methyl2-oxazolinium species 3, Derived from 1, Gave telechelic poly(N-acetylethylenimine) (5) having a hydroxyl group of different reactivity at both ends. Anionic polymerization of ethylene oxide induced by the lithium salt of 1, 7, produced a poly(ethylene oxide) macromer, 9, having a ringopening polymerizable 2-oxazoline group. The copolymer from 9 and 2-phenyl-2oxazoline, 10, has been shown to have good properties as a nonionic polymeric surfactant in which the N-benzoylethylenimine main-chain behaves as a lipophilic group whereas the oxyethylene graftchains act as a hydrophilic group. Di-salt 11 derived from 1 was polymerized to give polymide 13 (“amphi-ionic polymerization”).
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850302
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  • 312
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    Syntheses of N-(4-substituted phenyl)isocitraconimides and reactivities in their radical copolymerizations with styrene (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 479-488 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Radical copolymerizations of isomeric N-(4-substituted phenyl)isocitraconimides 7a-f and 9a-f (M1) with styrene (ST) (M2) were performed at 60°C, using 2,2′-azoisobutyronitrile as initiator in tetrahydrofuran, in order to study the substitutent effect on the copolymerization parameters. From the results, the monomer reactivity rations were determined as r1 = 0,0,81 ≤ r2 = 1,76 in the 7/ST systems, and r1 = 0, 0,27 ≤ r2 ≤ 0,42 in the system 9/ST. It was found that the relative reactivities (1/r2) of 7 toward the polystyrly radical cannot be correlated by the polar-substituent constant (σ) but by the resonance-substituent constant (ER) in the modified Hammett equation: log(1/r2) = ρσ + γER. Furthermore, the monomer reactivity ratios considering the influence of the penultimate effect were also determined, and the substituent effect of 7 and 9 was studied according to the above equation.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850306
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  • 313
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    UV-Photometrische Analyse kationisch erzeugter Polystyrole, 2Teil 1: cf.1.. Quantitative Bestimmung von Endgruppen in Polystyrolen, dargestellt mit Acylperchloraten (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 509-520 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Acyl perchlorates generated in styrene without a solvent by acyl chlorides and silver perchlorate gave polystyrenes with covalently bonded acyl groups. In order to gain secured values their number average relative molecular masses (M̄n) were determined by different methods. The polystyrenes could be hydrogenated with hydrogen and Raney nickel at room temperature and under atmospheric pressure without attacking the phenolic nuclei. In addition IR data and a UV absorption at 294 nm of the polystyrenes revealed the presence of and olefinic bond, which was also found in a polystyrene obtained by polymerisation with perchloric acid. Also the quantitative evaluation of the hydrogeneation by UV absorption data gave number average relative molecular masses (M̄n,H), which are in accordance with other M̄n values. Furthermore, the UV absorption data of the polystyrenes gave correct M̄n values (M̄n,e) in combination with the molar absorption coefficients (ε) of model compounds. The number of covalently bonded acyl groups in a polystyrene sample could be determined by quantitative measurement of the UV absorption in combination with the ε-values of model compounds and the M̄n values. This number was found to depend on the nature of the acyl perchlorate and it amounts to one acyl containing molecule per four to hundred molecules without an acyl group.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850309
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  • 314
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    Synthesis and properties of 9,10-dialkoxyanthracenes as fluorescent probes specific of polyolefins and their application to orientation measurement in polyethylene (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 541-548 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 9,10-Dialkoxyanthracenes with an even number of carbon atoms n in the aliphatic chain from n = 2 to n = 18 were prepared by reaction of the corresponding bromoalkanes with the sodium salt of dihydroanthraquinone. Ultra-violet and fluorescence spectra as well as life-times of the excited state of these different fluorescent probes were determined. Higher terms with n ≥ 8 proved to be valuable to measure the amorphous phase orientation in polyolefins.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850312
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  • 315
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    Dilute solution properties and unperturbed dimensions of poly(di-ni-alkyl itaconate)s (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 569-578 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The diesters of itaconic acid (methylenesuccinic acid) with higher C12 - C20 unbranched, saturated, aliphatic alcohols were prepared, purified, and polymerized in bulk or in solution with 2,2′-azoisobutyronitrile as initiator. The transparent to waxy polymers obtained were fractionated and all fractions characterized by viscosity and light scattering measurements. The Kuhn-Mark-Houwink-Sakurada relations were established and then extrapolated to thetaconditions, in order to calculate the unperturbed dimensions. High values of the steric factor σ, and the characteristic ratio C∞ were obtained. The results correlate well with those obtained previously for poly(di-n-alkyl itaconate)s from the corresponding lower C1 - C11 alcohols.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850315
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  • 316
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    CorrectionMakromol. Chem. 184, 1823 (1983) (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 615-615 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850319
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  • 317
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    Preparation of a polysulfone by polycondensation of disodium 4,4′-oxydibenzenesulfinate with 4-bromomethylbenzyl bromide (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 629-634 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polycondensations of 4-bromomethylbenzyl bromide (p-xylylene dibromid) (1) were carried out with 4,4′ -oxydibenzenesulfinate (3) in the presence of phase transfer catalysts, investigating the effect of reaction media, catalysts, monomer concentration, and reaction time. The polymer with the highest molecular weight was obtained at a monomer concentration of 8/15 mol/1 in nitrobenzene at 80°C for 48 h in the presence of tetrabutylammonium chloride. The characterization of the product by 1H NMR and IR spectra and by elemental analysis indicates the structure of a copolymer (5), containing both sulfinate and sulfone linkages in the main chain. Thermogravimetry of the product shows that its thermostability is lower than that of commercial poly(ether sulfone)s.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850402
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  • 318
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    Polymeric schiff's base chelates and their precursors, 7.Part 6: cf.29 Dioxygen binding and catalytic oxidation of 2,6-di-tert-butylphenol (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 669-685 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dioxygen binding and catalytic oxidation of 2,6-di-tert-butylphenol(9) were investigated by employing various low molecular chelates (1 and 2), covalently or coordinatively bound polymeric chelates (3, 4, 5, 6, and 7), and polymeric Schiff's base chelates (8). Particularly the covalently bound polymeric chelates 3 and 4 were found to exhibit activities similar to low molecular 1 in regard to dioxygen binding. It is suggested that these polymers can reversibly form mononuclear superoxo-complexes. In the oxidation of 9 the covalently bound polymeric chelates 3 - 5 exhibit good activity which does not decrease after repeated use.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850406
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  • 319
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    Untersuchungen zur klärung der sensibilisierten photodegradation von polystyrol in lösungen, 2Teil 1: cf. 1. EnergieübertragungsphänomeneZ. T. ausgeführt im Rahmen des Forschungsbereiches MR 1.9 - 1.4.3 der Polnischen Akademic der Wissenschaften. (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 725-747 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new approach is presented to explain “the sensitized photodegradation effect”, which was observed in polystyrene solutions irradiated with the light of a mercury lamp of wavelength λ ≥ 270 nm. The radiationless electronic excitation energy transfer from solvent molecules as energy donors to polystyrene (PS) macromolecules is considered to be the main factor influencing the polymer photodegradation rate in solution. Possible mechanisms of the energy transfer are discussed, the total energy transfer rate in eight investigated PS-solvent systems is evaluated and compared with PS photodegradation rates, determined by light scattering in the first part of this series.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850410
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  • 320
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    Polymer conformation and NMR chemical shifts, 9Part 8: cf.7. Poly(α-methylene-γ-butyrolactone) (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 771-786 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformational energies of poly(α-methylene-γ-butyrolactone) are calculated and compared with those of poly(methyl methacrylate). In spite of the structural resemblance of these two polymers, the patterns of the energy contour maps are clearly distinguishable from each other; the energy barriers between rotational isomeric states are appreciably higher in the former than in the latter polymer. The calculation indicates large non-bonded interactions between the protons in one lactone ring and those in the adjacent lactone rings. The broad NMR spectrum of poly(α-methylene-γ-butyrolactone) apparently reflects its rigid conformational structure. 1H and 13C NMR chemical shifts are calculated by theoretical shielding calculations based on conformational analysis. Much lower magnetic field resonances of the O—CH2 and α-CH2 carbons in poly(α-methylene-γ-butyrolactone) as compared with those of the O—CH3 and α-CH3 carbons in poly(methyl methacrylate) are well reproduced by the calculation. The shift to lower magnetic field is mainly attributed to paramagnetic shielding derived from the interaction between O—CH2 carbon and α-CH2 carbon. Tacticity- and conformation-dependent 1H and 13C NMR chemical shifts of poly(α-methylene-γ-butyrolactone) are well interpreted on the basis of the conformational analysis.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850414
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  • 321
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    Novel syntheses of alternating copolymers with amide and thioether linkages by polyaddition reactions of bifunctional cyclic iminoethers with dithiols (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1307-1316 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Alternating copolymers with amide and thioether linkages were synthesized by addition reactions of bisoxazolines 1a - 1f and bisoxazines 2a and 2b with dithiols 3a - c in aprotic polar solvents. The reactions of the aromatic bifunctional cyclic iminoethers such as 1a, 1c, 2a, and 2b with the dithiols 3a and 3c in N-methyl-2-pyrrolidone gave polymers with high molecular weight. However, the reactions of the aliphatic derivatives such as 1e and 1f with dithiols as well as the reactions of the bifunctional cyclic iminoethers with 3b led to polymers of low molecular weights. The reactions of methyl substituted bisoxazolines 1b and 1d with dithiols gave also polymers of low molecular weight.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850704
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  • 322
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    Thermodynamic and hydrodynamic properties of aliphatic polyesters, 2Part 1: cf.7.. Intrinsic viscosity, radius of gyration and second virial coefficient of poly(β-propiolactone) in 2,2,2-trifluoroethanol (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1361-1370 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular properties of poly(β-propiolactone) in 2,2,2-trifluoroethanol show that the poly(β-propiolactone) molecule is highly expanded in solution due to unusually large excluded volume effects. The values of the exponents in the relationships between the radius of gyration, the intrinsic viscosity, the second virial coefficient on the one hand and the molecular weight on the other agree viscosity, the second virial coefficient on the one hand and the moleculer weight on the other agree with those deduced by scaling arguments with the value of the universal critical (exponent) v ≈ 3/5.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850708
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  • 323
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    Interaction of cross-linked polyacrylic acid with cetyltrimethylammonium bromide (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1403-1408 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The interaction of cross-linked copolymers of acrylic acid with divinylbenzene (PAA-C-L) with the micelle-forming surface-active cetyltrimethylammonium bromide (CTMAB) is studied. It is shown that the ion-exchange interaction of PAA-C-L with CTMAB at small degrees of polyelectrolyte cross-linking is analogous to the interaction of linear polyacrylic acid with CTMAB. The total quantity of surface-active substances (SAS) bound to PAA-C-L increases with an increase of the SAS concentration in the solution, with the pH of the medium, and with the quantity of the binding agent in the ion exchange resin.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850712
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  • 324
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    Sodium metatungstate, a new medium for binary and ternary density gradient centrifugationIn memoriam Hans-Peter StockProfessor at the “Institute für Anorganische und Analytische Chemie der Freien Universität Berlin” from June 1971 to March 1978; deceased March 16, 1978. (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1429-1439 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sodium metatungstate, Na6[H2W12O40] is presented as a new medium for density-gradient centrifugation. This electrolyte may be used in aqueous, aqueous sodium chloride, or in methanol solutions. The sedimentation behaviour of sodium metatungstate in binary (Na6[H2W12O40]/H2O) and in ternary (Na6[H2W12O40]/NaCl/H2O) systems is presented and discussed. Practical examples are presented from macromolecular chemistry (Sedipur), biochemistry (DNA), and mineralogy (sodium-aluminium mica).
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850715
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  • 325
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    Segmented block copolymers of uniform chain length and defined structure, 2Part 1: cf.7.. Investigation of some physical propertiesDedicated to Professor H.-J. Cantow on his 60th birthday (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1469-1491 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Some physical investigations of segmented block copolymers of uniform chain length and defined structure and their constituents are described. Special attention was payed to the thermal behaviour of these new substances with respect 1. to the phase transformations in the solid and liquid state and 2. to the thermal stability of the materials. Several of these oligomers show phase transitions in the solid state. In some instances, the morphology of the solid material depends strongly on the sample history. The influence of the crystallization conditions is discussed. For the special case of esters of 4,4′-isopropylidenediphenol (bisphenol A) with isophthalic acid detailed investigations by dielectric and Brillouin spectroscopy of the glass-forming process are presented.
    Additional Material: 22 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850719
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  • 326
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    Metal-containing initiator systems, 35Part 34: cf.13.. Synthesis of block copolymers by using the binary initiator system cobaltocene/bis(ethyl acetoacetato)copper(II) (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1507-1516 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymerization of methyl methacrylate (MMA) with the binary initiator system cobalt-ocene (Co(C5H5)2)/bis(ethyl acetoacetato)copper(II)(Cu(eacac)2), was studied kinetically at 25°C in acetonitrile. The relationship between yield and molecular weight of the resulting poly(MMA) was suggestive of a living polymerization character in this system. The synthesis of block copolymers of MMA with styrene (St) was attempted by adding St as the second monomer to the polymerization system of MMA. The block copolymer was formed in a yield of 20% when MMA was polymerized for 1 day, while the yield went up to 80% when the MMA polymerization was carried out for 3 days. The resulting block copolymer was characterized by IR spectroscopy and gel-permeation chromatography.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850802
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  • 327
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    Microdomain structure of poly(styrene-4-vinylpyridine) diblock copolymers (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1169-1175 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of AB and BAB type poly(styrene-4-vinylpyridine) diblock copolymers with a sharp distribution of molecular weights were synthesized to study relationships between the molecular weight and domain size of lamellar and spherical microdomains. The domain sizes of diblock copolymer specimens cast from chloroform or 1,1,2-trichloroethane were estimated from transmission electron micrographs. As a result, the lameller domain spacings, predicted from Halfand's theory, agree well with the experimental results. The radius of spherical domains is far below the theoretical values predicted from Helfand's theory, though.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850610
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  • 328
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    Mikrokalorimetrische untersuchungen der enthalpischen wechselwirkungen von polymethylmethacrylaten verschiedener taktizität in lösung (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1199-1217 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Enthalpies of dilution, dissolution, and complex formation of atactic and tactic poly(methyl methacrylate)s (PMMA) were measured at 30°C with a heat flux microcalorimeter of TianCalvet. The enthalpies of dilution in 4-methyl-2-pentanone, toluene, and carbon tetrachloride are positive (endothermic). Because of different mutual interactions between the solvent molecules and the polymer segments they are dependent on the polarity of the solvent, on the concentration, the molar mass and the tacticity of PMMA, and on the temperature and time of annealing. The solution enthalpies are negative due to the enthalpy of the amorphous state of the polymer. They are also influenced by the parameters just mentioned and by the pretreatment of the PMMA probes. The exothermic stereocomplex formation between the iso-and syndiotactic triads can be determind quantitatively by the enthalpies of mixing of iso- and syndiotactic PMMA-samples. The enthalpy of complex formation is related to the mass of the isotactic triads and increases with growing excess of the syndiotactic triads in the sense of a completion of the complex formation of the isotactic triads.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850613
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  • 329
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    Thermodynamic properties of polylactones (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1235-1253 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Temperature dependences of isochoric heat capacity, temperatures and enthalpies of physical transitions for polyglycolide, poly(β-propiolactone), poly(γ-butyrolactone), poly(λ-valerolactone), poly(ε-caprolactone), polyundecanolactone, polytridecanolactone, and polypentadecanolactone were studied between 13,8 and (340 - 550) K in a vacuum adiabatic calorimeter within a limit of experimental error of about 0,2%. From the results obtained the functions H0 - H0 (O), S0 (T), and G0 (T) - H0 (O) were calculated over the range 0 to (340 - 550) K. Zero entropy of glassy polymers, Sg0 (O), and difference in zero enthalpies of glassy and crystalline states, Hg (O) - Hc0 (O), were estimated also. Regularities of changes in thermodynamic properties of polylactones, in dependence of the number of atomic groups in a repeating unit, were found that made it possible to evaluate the properties of some polylactones the corresponding experimental data of which are not known.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850617
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  • 330
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    Electrochemical preparation and characterization of poly(2,5-thiophenediyl) (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1295-1306 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A highly conductive poly(2,5-thiophenydily) film was obtained when thiophene was electrochemically polymerized at 5°C in nitrobenzene with Bu4NBF4 or Bu4NClO4 as a supporting electrolyte. A platinum plate or indium oxide glass was used as an electrode. The current efficiency was 62%. The IR, UV, and ESR spectra were compared with those of a poly(2,5-thiophenediyl) obtained from 2,5-dibromothiophene by polycondensation. The electrochemically prepared poly(2,5-thiophenediyl) was identified by its IR spectrum. In its UV spectrum, two bands are observed at 440 nm and 740 nm. The band at 740 nm disappears in an undoped film of poly(2,5-thiophenediyl), which resembles that of the polymer obtained by polycondensation. The ESR spectra were also measured for undoped and partly undoped films. The undoped film shows an asymmetrical signal, Whereas the signal of the polymer resulting from polycondensation is symmetrical. In the air the conductivity decreases by a factor of 10-2 of the initial value in about 70 days, but an undoped film is quite stable. The undoped film can be re-doped with iodine or sulfur trioxide and attains higher conductivity than the pellets of polymers obtained by polycondensation. This may be attributed to the difference in morphology.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850703
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  • 331
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    Functional metal-porphyrazine derivatives and their polymers, 12Part 11: O. Hirabaru, T. Nakase, K. Hanabusa, H. Shirai, K. Takemoto, N. Hojo, J. Chem. Soc., Dalton Trans., in press.. Synthesis and properties of polyimides containing a metalphthalocyanine ring and a pyridyl group (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1395-1401 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A novel class of polyimides (6a - c) containing Mt(II)-phthalocyanine rings was synthesized by solution condensation in N-methyl-2-pyrrolidone of Mt(II)-[2,9, or 10(or 2,16, or 17)bis(3,4-dicarboxybenzoyl)]phthalocyanine dianhydride [Mt(II)-dahPc: Mt(II) = Co(II), Ni(II), and Cu(II)] with 2,6-diaminopyridine, followed by thermal imidation. The polyimides showed room temperature dc-conductivities in the range of 10-12 - 10-9 Ω-1 · cm-1, and, after quaternization of the pyridine group, the conductivities increased by 1 to 3 orders of magnitude.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850711
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  • 332
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    Investigation of polyesters of adipic acid and sebacinic acid with hydroquinone by pyrolysis-mass spectrometry (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1449-1454 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure and thermal degradation behaviour of polyesters of adipic acid and sebacinic acid with hydroquinone were investigated by direct pyrolysis in the ion source of a mass spectrometer. Poly(oxyadipoyloxy-1,4-phenylene) (1) and poly(oxyebacoyloxy-1,4-phenylene) (2) undergo a cleavage of the ester bond as a very selective thermal degradation reaction (Eq. (iii)). In order to differentiate the thermal and electron impact induced degradation reactions of these polyesters the fragmentation pathways of corresponding low molecular weight esters were followed.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850717
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  • 333
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    Ethylene glycol oligomers (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1559-1563 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Pure samples of the oligo(ethylene glycol)s 1a (n = 30 or 45), were prepared from the monosodium salt (1c) and the ditosylate (1b) of pentadeca(ethylene glycol). The Melting points of the samples were found to be higher than those of comparable materials prepared hitherto. The melting points of several pure oligo(ethylene glycol)s in the range n = 9 to 45, deriving from this and earlier work, were compared with those of commercially available poly(ethylene glycol)s of similar average chain lengths.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850806
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  • 334
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    Télomérisation du chlorure de vinylidène, 1. Réaction avec le tétrachlorure de carbone par catalyse rédox (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1583-1595 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The redox telomerization of vinylidene chloride with carbon tetrachloride catalyzed by iron or copper salts was thoroughly studied. The DP of the telomers obtained vary from 1 to 100, roughly. The concentration of the reactants and the nature of the solvents exert some effect on the molecular weight distribution. The first adducts 1a - 1d (n = 1 to 4) were isolated and identified by NMR spectroscopy and viscosimetry.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850808
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  • 335
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    Kinetics of free radical polymerization of ortho- and para-alkylaryl esters of methacrylic acid (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1637-1646 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of free radical polymerization in bulk of alkylphenyl methacrylates with ethyl-,isopropyl and tert-butyl groups in the ortho- and para-positions of the phenyl ring with dilauroyl peroxide as initiator were investigated. For comparison and completion of the investigation, ortho- and para-tolyl methacrylates were reinvestigated with this particular initiator. Most of the results obtained do not obey classical kinetics of polymerization. The results were treated according to the concept of degradative chain transfer and it was concluded that this mechanism is responsible for the non-ideality. The ortho-substitution with increasing size of the substituents decreases the overall rate of polymerization and strengthens chain transfer to monomer.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850813
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  • 336
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    Thermisch und UV-photochemisch initiierte hochdruckpolymerisation des ethylens, 1. Molmassen-mittelwerte (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1685-1697 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ethylene is polymerized with thermal and with UV-photochemical initiation at temperatures between 130°C and 255°C up to pressures of 2500 bar. The conversions are between two and five percent. The degrees of polymerization as obtained from viscosity experiments are dependent on reaction temperature and pressure, but are insensitive to the kind of initiation, thermal or photochemical. These observations are explained by an equation which relates the degree of polymerization to kinetic parameters of the system which have partly been determined by independent experiments. From this equation, the activation energy and the activation volume of the transfer constant with the monomer, cm, are determined to be Ea(cm) = 43,9 ± 4 kJ · mol-1 and ΔV≠ (cm)=20,1 ± 3 cm3 · mol-1, respectively.
    Additional Material: 3 Tab.
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    The rubber elastic behaviour of crosslinked polymers and a critical consideration of theoretical conceptsDedicated to Prof. O. Wichterle on the occasion of his 70th birthday (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1751-1759 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The elastic properties in simple elongation have been investigated under various aspects for a series of elastomers, which were crosslinked randomly in the bulk state. The results are compared with different theoretical concepts for explaining the deviations from predictions of the simple statistical theory of rubber elasticity. The results do not favour clearly any one of the theoretical concepts under discussion.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850821
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  • 338
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    Equation of state for linear polymer melts: the chemical structure parameter and its relationship to the characteristic volume, packing densities, characteristic bulk modulus and glass transition temperature (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1767-1779 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is shown that the three-parameter equation of state for linear polymer melts, although consistent with the theorem of corresponding states, contains no information about the chemical structure of the polymer chain. This information is now included in the equation via a fourth parameter representing the structure. The relations between the chemical structure parameter and the characteristic volume of the polymer, its dense packing, characteristic bulk modulus, and glass transition temperature are deduced. It is demonstrated that the properties of the polymer are influenced by the compressibility of the polymer chain, which was not taken into account in the mechanical-statistical approaches to the equation of state for liquid polymers. It is also shown that the dense packing of a polymer is almost equal to the close packing of spheres. The determination of the parameters of the four-parameter equation requires the knowledge of the van der Waals volume of the constitutional repeating unit and p V T data for the liquid polymer, including the glassy transition region. This region should be investigated under cooling conditions considered as isochronal, the time of viscoelastic relaxations assumed to be zero.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850823
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    Epitaxy of helical polyolefins: Polymer blends and polymer-nucleating agent systems (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2043-2052 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Helical polyolefins (polypropylene (PP) and poly(1-butene)) (PB-1) possess crystallographic faces in which the side-groups form well aligned rows. These structural features are shown, through a number of examples, to interact with linear polymers (polyethylene (PE) and polyamides) and nucleating agents. These interactions explain, on the basis of characteristic epitaxial relationships, the mutual activity of certain pairs of crystalline polymers and the hitherto puzzling “universality” of some nucleating agents towards both linear (i.e. PE-like) polymers and helical polyolefins.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850924
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  • 340
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    Selective ring-opening polymerization of 3,5-anhydro-1,2-O-isopropylidene-α-D-xylofuranose synthesis of [3→5]-D-xylan (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2099-2107 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ring-opening polymerization of 3,5-anhydro-1,2-O-isopropylidene-α-D-xylofuranose was studied to investigate the selectivity of ring-opening mode under various polymerization conditions with a number of Lewis acids, anionic and coordinated catalysts. In all the conditions attempted here, the monomer attacks only the C-5 methylene carbon of the active end of the growing chain to form a stereoregular [3→5]-α-D-xylofuranan structure. With removal of the isopropylidene groups of the polymer, a new class of non-hydrolyzable polysaccharides, [3→5]-D-xylan, is obtained.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021851005
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  • 341
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    Quasielastic light scattering studies of the pressure-induced denaturation of lysozyme (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1441-1447 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The pressure-induced denaturation of lysozyme in acetic acid/acetate buffer at pH = 4,0 was studied in the pressure range 1 - 4500 atm (0,10 · 106 - 456 · 106 N/m2) by photon correlation spectroscopy. The hydrodynamic radius RH, initially independent of pressure, was at moderate pressures observed to pass through a minimum. At higher pressures, in the transition region, RH upon pressure denaturation was approximately 9%. This increase was significantly smaller than those reported from quasielastic light scattering measurements on lysozyme solutions utilizing chemical agents and temperature as denaturants. Speculative arguments for this behaviour are presented. Upon releasing the pressure the return of RH was not reversible. The influence of pressure on the mutual diffusion coefficient was studied for a low and a high concentration. The results indicate that there exist enhanced intermolecular interactions at higher concentrations.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850716
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  • 342
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    Sequence distribution and glass transition of vinyl alcohol/n-alkyl vinyl carbonate copolymers (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2153-2159 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 13C NMR spectroscopy was used for the determination of the sequence distribution in vinyl alcohol-ethyl vinyl carbonate copolymers prepared by reaction of poly(vinyl alcohol) with ethyl chloroformate. The 13C NMR spectra of the methylene carbons in the main chain show three split peaks whose intensities change with copolymer composition. These peaks can be assigned to the three dyad sequences. The obtained results show that ethyl vinyl carbonate units have an alternating tendency in the copolymer chain. The Tg values of the vinyl alcohol-ethyl vinyl carbonate and vinyl alcohol-butyl vinyl carbonate copolymers are influenced by both the overall copolymer composition and the monomer sequence distribution.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021851010
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  • 343
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    Gemischte Diester von 2,2′-Methylendiphenolen mit Methacryl- und Crotonsäure und ihre Polymeren. 13C NMR-Untersuchungen zur Strukturaufklärung (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2195-2204 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure of mixed diesters of three 2,2′-methylenediphenols with crotonic acid and methacrylic acid was studied by 13C NMR-spectroscopy. The position of the two acyl groups, expected from the synthetic pathway, was unambiguously confirmed by comparison with the corresponding mono- and diesters containing the same acyl group. In the same way, it was shown that the crotonoyl residue is not involved in the radical polymerisation of these esters.
    Additional Material: 4 Tab.
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    URL: http://dx.doi.org/10.1002/macp.1984.021851014
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  • 344
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    Investigations on linear segmented polyurethane elastomers, 1. Temperature dependence of microphase segregated structure (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2233-2240 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The temperature dependence of microphase segregation in polyester and polyether segmented urethane elastomers has been studied by small-angle X-ray scattering, viscoelasticity, and infrared spectroscopy. The mean-square electron density fluctuations distincitly decrease with increasing temperature above about 60°C. Their value estimated from the location of the first peak of the electron density correlation function increases with increasing temperature; at the same time the peak becomes flat and finally disappears. The infrared absorbance for the NH vibration decreases above about 80°C. These results correspond to an increase of the mean distance between the centers of the nearest neighbouring microdomains, mainly composed of the hard segments, and to intermixing of hard and soft segments in the boundaries of the domains by heat treatment. This fact suggests that a domain structure is formed by casting in these polyurethane elastomers. The dynamic storage moduli G′ for both samples investigated decrease in the two temperature ranges, -70 to -20°C and 60 to 120°C, the former corresponds to the dispersion of soft segments and the latter to the dissociation of hydrogen bonds.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021851017
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  • 345
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    Polyether-segmented polyamides as a new designed antithrombogenic material: Microstructure of poly(propylene oxide)-segmented nylon 610 (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2259-2267 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of segmented polymers based on poly(propylene oxide) (PPO) and nylon 610 was characterized. Transmission electron microscopic observations revealed spherulitic structures similar to those of semicrystalline homopolymers. Dynamic mechanical measurement and thermal analysis suggested distinct phase separation between the PPO and polyamide segments, which is generally observed for amorphous block copolymers systems. Moreover, density and X-ray diffraction measurements indicated that the crystallization of the polyamide segments is promoted by the introduction of PPO segments in the copolymer. This is probably correlated with unique growth of crystalline lamellae in the PPO-segmented polyamides.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021851103
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  • 346
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    Etude par résonance magnétique nucléaire du 1H et 13C des télomères du chlorure de vinyle et du tétrachlorure de carbone (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2001-2009 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The adducts and bi-adducts of the reaction of vinyl chloride with carbon tetrachloride, CCl3—(CH2CHCl)n—Cl and Cl—(CHClCH2)—CCl2—(CH2CHCl)p—Cl respectively, have been studied by 13C and 1H NMR. The identification of the characteristic peaks of each product enables of much better control of the purity of the telomerization reactions. Moreover, it was possible to resolve complex spin systems in 1H NMR (up to 9 non-equivalent spains). In particular the threo and erythro conformation of the tri-adducts could be assigned without any ambiguity. Thanks to model molecules, the chemical shifts were specified in 13C NMR for all carbon atoms with similar groups.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850920
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  • 347
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    Asymmetric induction copolymerization of isobutyl vinyl ether with indene by (-)-menthoxyaluminium dichloride and (-)-menthoxytitanium trichloride (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2053-2064 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The copolymerization of isobutyl vinyl ether with indene was carried out with (-)-menthoxyaluminium dichloride (1) and (-)-menthoxytitanium trichloride (2) as initiators. Although optically active copolymers were obtained in the copolymerization in non-polar solvents, the copolymers prepared in a polar solvent was optically inactive. From the linear relationship between the optical rotation and the diad probability P2 (m1 m2) of the copolymers, it was found that asymmetric carbon atoms were introduced in vinyl ether monomeric units but not in indene ones.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021851001
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  • 348
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    Synthesis of segmented copolyamides by using telechelic prepolymers (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2077-2087 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyamide-polystyrene and polyamide-poly(oxyethylene) segmented copolymers 6a, b of well-defined structure and composition were synthesized using telechelic prepolymers. α,ω-Dicarboxyl-terminated polystyrene 2 was prepared by radical polymerization of styrene initiated by 4,4′-azobis(4-cyanovaleric acid) (1). α,ω-Dicarboxyl-terminated poly(oxyethylene) 3 was prepared by the reaction of commercially available hydroxyl-terminated poly(oxyethylene) with excess succinic anhydride. These telechelic prepolymers were condensed with hexamethylenediamine in a 1:1 mole ratio together with nylon-6,6 salt using the triphenyl phosphite/pyridine system. Similarly, α,ω-diamino-terminated polystyrene 5 was prepared and condensed with adipic acid and nylon-6,6 salt. The segmented copolymers 6a and 6b were characterized by their 1H NMR and IR spectra.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021851003
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  • 349
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    Propylene polymerization on titanium-magnesium catalysts, 3.Part 2: cf.2. Influence of the products resulting from the interaction of trialkylaluminium with aromatic esters on the activity and stereospecificity (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2377-2385 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of the conditions of interaction between AlR3 and aromatic esters (D) and of the products formed on the activity and stereospecificity of the actalytic system TiCl4/ethyl benzoate/MgCl2 + Al(i-Bu)3 + D in propylene polymerization was studied. An increase of the polymerization temperature above 60°C leads to a decrease in the activity of the titaniummagnesium catalyst (TMC) and in the isotacticity of the polypropylene produced. A preliminary interaction of AlR3 with D at elevated temperatures diminishes the isotacticity of the polymer and has no influence on the activity of TMC. IR spectroscopy was employed to study the influence of the temperature and time of AlR3 interaction with the esters as well as that of the composition of AlR3 (AlEt3 or Al(i-Bu)3) on the process of reduction of these esters. Reduction products such as aldehydes, ketones, and primary alkoxy derivatives of aluminium cannot provide of high stereopecificity of TMC. High stereospecificity is rather thought to be provided by the interaction of active sites with a free ester or tertiary alkoxy derivaties of aluminium. The contribution of each of these processes depends on the catalyst composition and on the polymerization conditions.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021851115
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  • 350
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    The role of CT monomer complexes in radical copolymerization (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2411-2420 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanism of the copolymerization of monomers forming a charge-transfer complex in the reaction mixture was investigated. A condition for establishing a certain mechanism consists in the determination of the elementary rate constants of the copolymerization; the results are in good agreement with well-known elementary rate constants for radical polymerization. We could prove the mechanism by the method of Giese producing radicals in high concentrations. The radicals react either with monomers or monomer pairs, and the initiating radicals obtained are subsequently transferred into the hydrogenated form. The initial reaction products were identified by gas chromatography. Only addition to the radicals of either maleic anhydride or styrene and not of the CT-complex was established by the reaction products in the mixture of styrene with maleic anhydride.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021851118
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  • 351
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    The adsorption of divalent metallic ions by polyamides having oligo(oxyethylene) segments in the repeating unitDedicated to Professor Dr. Volker Jaacks (decreased 1971 in the Himalayas) on the occasion of his 50th birthday (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2437-2441 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyamides 1a - d having 1 to 4 oxyethylene units in the repeating unit were prepared from α-(2-aminoethyl)-ω-aminooligo(oxyethylene)s (2a - d) and sebacoyl chloride. The adsorption of divalent metallic ions by the polyamides 1 was found to be in general in the order: Cu2+ 〉 H2+g ≫ Zn2+ ∼ Cd2+. Polyamides with longer oligo(oxyethylene) units exhibit better adsorption capacities. The adsorption of Hg2+ by a polyamide with four oxyethylene units in the repeating unit follows a Langmuir adsorption isotherm, with a binding constant of K = 146 1 per mol of repeating units and a maximum Hg2+ adsorption of ws = 0,36 mol per mol of repeating units.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021851121
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  • 352
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    The sedimentation behaviour of polystyrene in various solvents in semidilute solutions (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2459-2465 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sedimentation coefficients of S of polystyrene covering a broad range of molecular weights M, are measured in toluene and 2-butanone in the semidilute regime. The results are compared with literature data using a plot of S · NA · η/(1 - νρ) = M · η/f versus concentration c, allowing experiments in different solvents of different density ρ and viscosity η to be compared (ν: partial specific volume of polymer; f: friction coefficient; NA: Avogadro number). According to scaling theory for concentrations higher than a critical concentration c, linear plots are to be expected. This is true for the theta-solvent cyclohexane, but for the theta-solvent cyclopentane as well as for the thermodynamically semi-good and good solvents bent curves are obtained, the slopes of which turn toward a limiting value for high M and low c. The theoretical values of the slope for theta-solvents (-1) is well represented by both theta-solvents. For the semi-good and good solvents the experimental limiting slopes are (slightly) lower than the predicted ones. With samples of still higher M becoming available this difference might become more pronounced.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021851124
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  • 353
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    Induction of metachromasia and circular dichroism in some dyes by sulfated bael gum polysaccharide and its anticoagulant property, 1 (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2241-2251 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Bael (Aegle marmelos) gum polysaccharide (AMA), a polyacid polysaccharide with a high equivalent weight (2091) was shown to exhibit a very weak chromotropic character and to fail to induce a metachromatic spectral shift of the dye toluidine blue. Sulfation of the polysaccharide to a carboxylate/sulfate mole ratio of 1 (AMA-S2; equivalent weight 698) largely enhances the chromotropic character. AMA-S2 shows a blue shifted metachromasia with toluidine blue (TB) and pinacyanol chloride (PCYN), and a red shifted J-band with N,N′-diethylpseudoisocyanine chloride (PIC). Mixtures of AMA-S2 with both PCYN and PIC exhibit a strong circular dichroism in the visible range of the respective dye/polyanion system. The anticoagulant property of the Bael gum polyasaccharide also improves with its sulfation, as expected.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021851101
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  • 354
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    Conformational analysis and reactivity in isotactic specific polymerization of C-3 branched α-olefins (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2599-2608 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Quantitative conformational analysis of 3-methyl-1-butene, 3-methyl-1-pentene and 3-ethyl-1-pentene seems to support the hypothesis that the conformation of these monomers in the active state of Ziegler-Natta isotactic polymerization is either H-skew + or H-skew -. It seems, however, that the experimentally determined reactivities of the considered α-olefins in the initiation steps of the isotactic polymerization could be accounted for quantitatively only by assuming somewhat different activation energies for the attack of the different monomers.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021851211
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  • 355
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    Thermodynamic and hydrodynamic properties of aliphatic polyesters, 3.Part 2, cf. 6. Analysis of osmotic and light scattering data of poly(β-propiolactone) in 2,2,2-trifuloroethanol in terms of a universal scaling law for the osmotic pressure in the excluded volume limit (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2401-2410 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Osmotic and light scattering data of poly(β-propiolactone) in 2,2,2-trifluoroethanol, a thermodynamically very good solvent, are analyzed in terms of a universal scaling law for the osmotic pressure in the excluded volume limit. The polymolecularity correction function to calculate osmotic pressures from light scattering data is deduced and a numerical method to treat simultaneously all the measured osmotic pressures at different concentrations is developed. It is shown that, for a given concentration, provided the molecular weight of the polymer species together with its radius of gyration is known, the osmotic pressure of its dilute and semidilute solutions can be calculated.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021851117
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  • 356
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    Ethylene-propene copolymerization in the presence of a 13C enriched catalyst: End group analysis and monomer reactivities in the first insertion steps (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2421-2428 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ethylene and propene were copolymerized in the presence of an isotactic specific 13C enriched catalyst. The 13C enriched end groups in the copolymers were detected by 13C NMR analysis. The resonances of the enriched carbons of the end groups could be assigned and the relative reactivities of the monomers in the insertion steps occurring at the beginning of the copolymerization were determined.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021851119
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  • 357
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    Kinetics of deactivation in the BuOTiCl3/AlEt2Cl initiated polymerization of styreneNCL Communication No. 3472. (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2443-2449 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The deactivation of the catalytic activity of the BuOTiCl3/AlEt2Cl initiated polymerization of styrene in heptane was found to follow a second-order rate law. The varying slopes in the second-order plots observed with varying catalyst concentrations are due to the heterogeneous nature of these colloidally dispersed catalysts. Site poisoning by reversible adsorption of the AlEtCl2 formed, is proposed as the probable reason for the deactivation.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021851122
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  • 358
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    Structural studies on molecular complexes of polyethers, 3.Part 2: cf.11. Urea-polyether complexes (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2467-2473 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Complexes of urea with polyethers, \documentclass{article}\pagestyle{empty}\begin{document}$\rlap{--} [\left( {{\rm CH}_2 } \right)_m {\rm O\rlap{--} ]}_n$\end{document} (m = 2-4, 6, 8-10), were prepared, and their crystal structures and decomposition temperatures were studied. The crystal structures of the complexes with polyethers (m ≥ 3) are similar to those of n-alkanes, so-called urea adducts. Only poly(oxyethylene), (m = 2), presents a complex of a different type of crystal structure. The decomposition temperatures of the complexes are in the range of 134 to 144°C and change in parallel with the melting points of polyethers themselves against the number of CH2 groups in the monomeric units.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021851125
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  • 359
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    Phase transfer catalysed reaction between chloromethylated poly(styrene-co-divinylbenzene) and the superoxide radical anion (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2511-2516 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reaction of chloromethylated poly(styrene-co-divinylbenzene) (1 wt.-% of divinylbenzene) with potassium superoxide in the presence of phase-transfer catalysts was studied. It was found that in dimethyl sulfoxide and in the presence of 18-crown-6, the hydroxymethylated polymer is the main product with a yield of 45%. In dimethylformamide the transformation of chloromethyl groups was found to be the highest, but only 60% of alcohol groups are present in the resulting product. In benzene the transformation reaches only 25%. With Bu4NI as catalyst in a mixture of solvents, the transformation of chloromethyl groups proceeds with 85% yield and the product contains 80% hydroxyl groups.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021851203
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  • 360
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    Intrinsic viscosity versus molecular weight relationship of polystyrene in cis-decahydronaphthalene (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2619-2623 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Intrinsic viscosities [η] and mean-square radii of gyration 〈RG2〉 of a polymer homologous series of commercially available narrow-molecular-weight-distribution polystyrene (PS) samples in a molecular-weight range of 800 up to 24 · 106 were determined in cis-decahydronaphthalene at 25°C by light-scattering and viscosity measurements. These dilute solution properties were compared with those for PS in the good solvent toluene, in the constitutional isomer trans-decahydronaphthalene both at 25°C and in cyclohexane at 34,5°C as a theta-system.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021851213
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  • 361
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    X-ray investigations on liquid crystalline side chain polymers (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 6 (1984), S. 31-39 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray investigations have been carried out on crystalline and smectic polymers with polysiloxane backbones and mesogenic side groups attached to the main chain by flexible alkyl spacers. Fibers suitable for obtaining high-quality X-ray patterns of crystalline and smectic phases were produced by stretching samples, in which case the main chains were oriented or, with even better success, by alignment of the polymer side chains in a magnetic field. Ordered domains were detected for the crystalline and smectic state which were differently oriented depending on the fiber producing procedure. However, the packing of the chains within the domains is unaffected by the alignment procedure. The packing of the crystalline phase differs little from commonly known polymeric systems, and the smectic phase can be described with the same kind of packing in a less ordered state.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.020061984103
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  • 362
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    Some problems in the field of organosilicon block copolymers (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 6 (1984), S. 77-91 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Conditions of the synthesis of oligoorganocyclosiloxanes of the bead-like and polycyclic structure were studied. On the basis of synthesized oligomers the corresponding block copolymers were obtained by the reaction of heterofunctional condensation with α,ω-diamino(dichlor)diorganosiloxanes. Thermomechanical, thermogravimetric, Roentgenographic, and electronmicroscopic studies of block copolymers show that their properties are determined by a ratio of lengths of linear and polycyclic fragments in the chain. When the lengths of linear and polycyclic fragments have definite values, the microheterophase structure is observed in synthesized block copolymers.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.020061984107
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  • 363
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    Meander model of amorphous polymers (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 6 (1984), S. 163-194 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A review of the present state of the meander cube model of amorphous polymers is presented. It is mainly concerned with appropriate methods for the determination of 3r/d, the meander cube side length (measured in lateral chain distances d). Some recent results are also presented:(a) on the magnetic birefringence of Polystyrene-solutions, which can be explained by a similar cubic superstructure of the solution (with a little smaller cube side length than in the condensed polymeric state) down to a few percent of concentration.(b) on the π/A-isotherms of some polymer thin films cast from dilute solutions, which indicate the existence of either a cube-meander monolayer (e.g. for Polystyrene) or a monolayer of 2-dimensionally superfolded molecules, with the monolayer partially folded in the third direction, forming layers of 3r in height (e.g. for IR, NBR).
    Additional Material: 31 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.020061984112
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  • 364
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    Synthesis and some properties of polyorganocarbosiloxanes of cyclolinear structure (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 6 (1984), S. 227-233 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Carbosiloxane polymers of cyclolinear structure have been synthesized by hydrosilylation reaction. The structure of the elementary unit is determined by the structure of organocyclotetrasiloxanes, which have groups in 1,3- and 1,5-positions. The investigation of the polyaddition reaction has shown that cyclotetrasiloxanes with 1,5-position of reactive groups yield polymers with molecular weights till 25·104, contrary to tetrasiloxanes with 1,3-position. This is connected with a higher reactivity of the former cyclosiloxane. The morphology of the polymers depends on the linking mode of cyclotetrasiloxanes in the polymer chain. The X-ray and electron-microscopic investigation have shown that the polymer from I + III crystallize during polyaddition; the degree of crystallinity of these polymers is 30 and 50%, respectively. The thermomechanical properties of the resulting cyclolinear polymers have been also investigated.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.020061984116
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  • 365
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    Polymeric monolayers and liposomes as models for biomembranesThis contribution is an extended abstract of a paper presented at the FRG/USSR-Symposium in Taschkent 1983. It will be published in details elsewhere (Advances in Polymer Science, 1984).. How to bridge the gap between polymer science and membrane biology? (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 6 (1984), S. 245-258 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This contribution deals with the stabilization of membrane model systems, especially vesicles. The desired further biological functionalization of these stabilized polymeric membranes is possible via the incorporation of proteins. Addition of natural lipids to polymerizable membranes and degradation of the unpolymerized component after polymerization allows selective opening of otherwise stable compartments. Finally, first attempts are made to combine biological properties of natural cells and the durability of polymerized membranes via fusion of synthetic vesicles with natural cells.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.020061984119
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  • 366
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    Diffusion model of volume recovery in glasses (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 6 (1984), S. 305-315 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Four most prominent features of the volume recovery in glasses of different nature, including polymeric ones, such as non-linearity, asymmetry, memory effects and hysteresis phenomena are analyzed on the basis of a simple diffusion model. The kinetics of the structural recovery is assumed to be controlled by the diffusion of free volume in a sample. Thus, the above mentioned effects are referred to specific evolution of the spatial distribution (profile) of the free volume. Apart from this, the dependence of diffusion coefficient D on the free volume fraction f is introduced for the correct description of the experiments. Computer simulations of the corresponding experiments have been performed using functions D (f) of different types: D = A·exp (-B/f), D = A·exp (B.f) and D = A·fn. The curves of the volume recovery and the corresponding profiles of the free volume in samples have been obtained as a result of computation. All these results are shown to coincide quantitatively with the available literature data on the volume recovery and to be practically independent of the choice of D (f) function type.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.020061984123
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  • 367
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    Novel coal based monomers and thermally stable polymers (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 7 (1984), S. 17-29 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Developments in the synthesis of thermally stable polymers have been discussed, attention being paid to the synthesis of some novel polymers with naphthalene and binaphthalene recurring units. Unconventional organic raw material, i.e. coal tar, has been recognized as suitable monomer source for the production of such polymers.The synthetic routes and properties of novel poly[bis(benzimidazo-benzisoquinolinones)], poly(naphthalimides), poly[oxyarylenebis(acenaphthalene)quinoxalines] and crosslinked polymers with similar structural repeating units have been demonstrated.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.020071984102
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  • 368
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    Functional polymersA. C. Albertsson, D. A. Bansleben, E. Borsig, P. Grosso, Z. Janovic, M. Kitayama, S. J. Li, J. Muggee, C. Nir, Y. Okahata, W. Pradellok, M. Purgett, F. Xi. (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 7 (1984), S. 1-15 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Functional polymers have become of major importance in the development of polymer science (1). These polymers have as their primary characteristics the properties of the functional groups and not so much the macromolecular properties. Functional polymers have become of interest in biology and medicine, in energy production and conservation, in agriculture, in food production and preservation, in nutrition and health care. They are prepared by homo- and copolymerization involving functional monomers or by substitution reactions on already formed reactive polymers. Conventional methods and novel approaches are being used to accomplish new designs in macromolecular architecture and to tailor-make multipurpose new polymeric structures.
    Additional Material: 13 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.020071984101
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  • 369
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    Recent developments in the polymerization of olefins with organometallic catalysts (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 7 (1984), S. 41-61 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Some recent developments in basic research on the polymerization of olefins to linear polymers are reviewed, including progress in preparation of catalytic systems, advances in knowledge about the mechanism of polymerization and attempts to control molecular weight distribution.For the catalytic systems of the type TiCl4/MgCl2/AIR3/Lewis bases indirect methods for the characterization of the active centers are considered. Dissimilarities in the time dependence of the rate of polymerization and changes in the productivity as a function of the Lewis base-to-aluminum alkyl ratio indicate that ethylene and propylene polymerize, at least in a large part, on different active centers. However, productivity of the highly stereospecific centers synthesizing isotactic poly(α-olefin)'s is of the same order of magnitude for ethylene and propylene.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.020071984104
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  • 370
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    Structural aspects of mechanical destruction of oriented polymers (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 7 (1984), S. 147-169 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relation between the structure and mechanical fracture of oriented polymers is discussed. The fracture behaviour originates from the structural heterogeneity of polymers, i.e., the presence of micro- and macrofibrils, alternating crystalline and disordered (amorphous) regions along microfibrils etc. The fracture behaviour of polymers is analyzed in terms of the kinetic thermal-fluctuation concept of strength of solids. The phonon mechanism of nucleation of the breaking thermal fluctuations in disordered regions of microfibrils is discussed. A critical role played by kink band formation in the appearance of localized submicro- and microcracks is elucidated. The mechanism of propagation of the main crack is revealed through studies of the electron microscopic fractograms from the rupture surfaces of fibers. The need for an analysis of the polymer fracture in terms of the nonequilibrium systems' theory is emphasized.
    Additional Material: 20 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.020071984109
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  • 371
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    New polymers and polymer derivatives by cationic techniques. Combination of controlled elementary steps (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 7 (1984), S. 171-199 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Some key concepts available to the macromolecular engineer have been outlined. In addition to useful ultimate properties the macromolecular engineer has also to consider convenient processing characteristics. The way toward these objectives is by combining of elementary events, by exploiting the mechanistic understanding of controlled ion generation cationation/propagation and termination. Figure 14 outlines and combines some of the elements considered, and shows some representative structures that can be synthesized by utilizing carbocationic macromolecular engineering concepts.
    Additional Material: 14 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.020071984110
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  • 372
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    Polymere ammoniumsalze aus N,N,N′,N′-tetramethylalkylendiaminen und N,N′-alkylenbis(chloracetamid)en (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 239-247 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Long chain polymeric ammonium salts 3a-g and 4a were prepared in DMF/H2O from N,N,N′,N′-tetramethylalkylenediamines 2a and 2b and N,N′-alkylenebis(chlorocetamide)s 1a-g. Some of them can be casted to clear transparent sheets. The chlorine atoms in 1a - g are activated by the adjacent carbonyl amino group. The polymer from N,N′-tetramethylenebis(chloroacetamide) (1d) and N,N,N′,N′-tetramethylhexamethylenediamine (2b) shows an intrinsic viscosity of 61 ml/g, the highest value known for polyelectrolytes so far. The intrinsic viscosity decreases with increasing numbers of CH2-groups in the monomers. The polymeric ammonium salts 3a - g and 4a give sheets from DMF solutions, which are soluble in water and stable under normal conditions. Polymers which are best suitable for the preparation of sheets show less hygroscopicity than the others, due to their structure. Intrinsic viscosities were calculated from the reduced specific viscosities measured in 0,4 M KCl but may be also determined in water by the method of Yuan et al., plotting the reduced specific viscosities as a function of 1/√c.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850202
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  • 373
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    Systèmes réactifs polyuréthannes bloqués, 1. Dissociation thérmique en fonction du type d'isocyanate et du type d'agent de blocage. etude par DSC et IRTF (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 281-295 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The preparation of blocked isocyanates and their thermal dissociation into isocyanate and blocking agent was studied by DSC and IR spectroscopy. Thermal deblocking was found to be possible only with isocyanates blocked with ε-caprolactame or 2-butanone oxime, but not with β-ketoesters. With 2-butanone oxime  -  the most convenient blocking agent  -  the dissociation of blocked aromatic isocyanates starts at ≈ 80°C and is fast at 120°C. With blocked aliphatic isocyanates, the temperature of dissociation (Td) is higher (≈ 120°C). Ether or tertiary amines have only a poor catalytic effect on the dissociation, and metal naphthenates have no apparent effect. The thermal and viscosity properties of prepolymers with terminal blocked isocyanate groups were investigated. The molecular interactions decrease in the order 1,4-phenylene diisocyanate (7) ≫ 4,4′-methylenediphenylene diisocyanate 〉 trans-1,4-cyclohexylene diisocyanate ≈ 2,4- and 2,6-toluene diisocyanate.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850206
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  • 374
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    Detection of a transition in diluted solution: polymer/solvent/non-solvent mixtures (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 339-345 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The behaviour of poly(N-vinylcarbazole) (PNVC) in dilute solution of chlorobenzene/methanol and 1,3-dichlorobenzene/methanol mixtures was studied. Theta compositions at 298 K were determined by using the cloud-point method, giving values of 14, 1 vol.-% methanol and 15 vol.-% methanol, respectively. In both cases, viscometric measurements confirmed that the polymer was in the unperturbed state. A variation of several thermodynamic parameters, KΘl,γ and B with the solvent mixture composition and a transition in the coil state were detected at 5,0 vol.-% methanol for the PNVC/chlorobenzene/methanol system and at 7,5 vol.-% methanol for the PNVC/1,3-dichlorobenzene/methanol system.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850210
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  • 375
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    Liquid-liquid phase separation in multicomponent polymer systems, 21.Part 20: cf.: M. H. Onclin, L. A. Kleintjens, R. Koningsveld, Br. Polym. J. 12, 221 (1980). Deuterium isotope effect in polymer compatibilityDedicated to Professor H.-J. Cantowon the occasion of his 60th birthday (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 377-387 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The spinodal and, hence, the miscibility gap of relatively short chain polystyrene/polybutadiene (PS/PB) mixtures is shifted by 14°C towards higher temperatures, if the hydrogen in PB is replaced by deuterium. The shift corresponds to a difference in the heat of mixing of about 0,2 kJ per mole of styrene units for a 1:1 PS/PB mixture. The effect has been observed by means of Gordon's Pulse Induced Critical Scattering method and the resulting spinodals are found to differ also with respect to the location of their maximum which indicates disparity in the entropy of mixing. For the prediction of the spinodal in a polystyrene/polybutadiene/perdeutereous polybutadiene (PS/PBH/PBD6) system the assumption of non-athermal mixing in PBH/PBD6 is needed. The value estimated for the PBH/PBD6 interaction parameter involves the second viral coefficient for solutions of PBD6 in PBH to be very close to zero. Expressions are presented for the second virial coefficient in quasiternary systems by scattering methods.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850214
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  • 376
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    IR-und UV-spektroskopische Eigenschaften einer homologen Reihe von molekulareinheitlichen, 12gliedrige Ringe enthaltenden LeiteroligomerenHerrn Prof. Dr. G. Manecke, Berline, gewidmet (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 499-508 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reactions of multiple acrylates of oligo[(hydroxyphenylene)methylene] s (2a-2f), strongly diluted in boiling benzene, with 2,2′-azoisobutyronitrile in a mole ratio of 1:10, were investigated. The elemental analysis and the determination of relative molar masses of the resulting products (3, 4, 5, 6a, 6b, 7a and 7b) demonstrate that their molecules contain two nitrile groups. These data, together with the IR and UV spectra, show that the products are molecularly uniform ladder oligomers with two 1-cyano-1-methylethyl groups on both ends.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850308
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  • 377
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    Synthesis and X-ray photoelectron spectroscopy of poly(α-ethyl-α-methyl-β-propiolactone) terminated with a perfluoroalkyl group (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 579-586 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Perfluorinated carboxylates are efficient initiators of the α-ethyl-α-methyl-β-propiolactone polymerization resulting in perfluoroalkyl-terminated polyester. The X-ray photoelectron spectra of the C8F17-end-capped polyester agree with an enrichment in fluorine atoms of the surface layer corresponding to an average number of 7 perfluoro groups per chain or to 36,6 wt.-% of C8F17-groups instead of 8,4 wt.-% as calculated for a random distribution.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850316
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  • 378
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    Phase separation by synthesis of semi-interpenetrating network on the basis of polystyrene and poly(butyl methacrylate) from homogeneous solution (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 347-351 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Phase separation by semi-interpenetrating polymeric network formation based on the copolymer styrene-divinylbenzene (PS-DVB) and poly(butyl methacrylate) (PBMA) was investigated by light scattering. The time for phase separation was measured as a function of the rate of the copolymerization reaction and of the composition of the initial blend. The time until the outset of phase separation decreases with increasing content of PBMA in the blend. The change in concentration of DVB does not influence the process of phase separation.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850211
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  • 379
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    Studies on the CHCL3-soluble fraction of polythiophene and its conductivity on doping with iodine (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 389-396 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The CHCl3-soluble fraction of polythiophene, prepared by catalytic coupling of thienyl Grignard reagent, was characterized by VPO, GPC, TLC, 1 H NMR, and WAXS measurements. Iodine doping of this polymer shows a maximum conductivity of the order of 5 Ω-1· cm-1, much higher than that of I2-doped compact powder pellets of the insoluble polymer. IR spectra of slightly I2-doped polythiophene show two new strong absorption bands, one at 1360-1380 cm-1 and the other at 1140 cm-1. XPS results indicate that the C 1st peak does not change after doping while the profile of the S 2p peak changes markedly. This suggests that in I2-doped polythiophene the positive charge is localized on the S atom. Combined results of the change of the I 3d XPS peak profile and the Raman spectrum in the low frequency region suggest that iodine in doped polythiophene is present in the form of the I2 moleculre and the I-ion, in contrast to polyacetylene where iodine exists in the form of I3- and I5- anions.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850215
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  • 380
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    Préparation de polystyrène de masse éalevée à chaîcne aliphatique ou noyaux aromatiques deuteriés (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 453-458 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Isotopically substituted styrene, (phenyl-2H5) styrene (3), and selectively labled styrene, [alpha;, beta;-2H2] styrene (6), were prepared by the classical two step synthesis, starting with the correspondingly labeled compounds. By anionic polymerization in an inert atmosphere labeled high molecular weight polystyrences 10 and 11 were prepared.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850303
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  • 381
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    The influence of molecular interaction on polymerization, 8.Part 7: cf.4. Copolymerization of monomethyl itaconate with 2-naphthyl methacrylate (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 353-362 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The copolymerization of monomethyl itaconate (monomethyl 2-methylenesuccinate, MMI) with 2-naphthyl methacrylate (2-NM) initiated with 2, 2′-azoisobutyronitrile (AIBN) in solvents of different dielectric constants and capability to form hydrogen bonds was investigated. The reactivity ratios of the monomer pairs in the different solvents are as follows: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {{\rm in chloroform:}} \hfill & {r_{{\rm MMI}} = 2,44 \pm 0,19{\rm and }r_{2{\rm - NM}} = 1,20 \pm 0.28} \hfill \\ {{\rm in 1,4 - dioxane:}} \hfill & {r_{{\rm MMI}} = 0,49 \pm 0,04{\rm and }r_{2{\rm - NM}} = 0,97 \pm 0.29} \hfill \\ {{\rm in acetone:}} \hfill & {r_{{\rm MMI}} = 0,15 \pm 0,00{\rm and }r_{2{\rm - NM}} = 0,28 \pm 0.03} \hfill \\ {{\rm in acetonitrile:}} \hfill & {r_{{\rm MMI}} = 0,10 \pm 0,01{\rm and }r_{2{\rm - NM}} = 0,35 \pm 0,14.} \hfill \\ \end{array} $$\end{document}IR and 1H NMR spectroscopy studies show the influence of the solvent on the capability of the monomers to form hydrogen bonds and donor-acceptor associates. The changes in the reactivity ratios of both monomers are attributed to the interaction observed between the monomer molecules as well as between the molecules of the monomers ad the respective solvent.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850212
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  • 382
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    A neutron diffraction study on the doping of polyacetylene by AsF5 (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 397-416 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The doping of deuterated polyacetylene (cis and trans) with AsF5 was studied by neutron diffractometry. A method of optimize the crystallinity of the doped material is described. Evidence for the presence of two species in the doped polymer which are probably AsF6- and AsF3 is presented. Model calculations based on a series of [CDxH1-x(AsF5)y]n samples support a “first-stage” intercalation structure with a graphitic structure.
    Additional Material: 21 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850216
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  • 383
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    Oxydation photothermique d'élastomères de polyuréthannes thermoplastiques, 4Parties 3: J.-L. Gardette, J. Lemaire, Polymer Degradation and Stability 6 (1964).. Influence d'un oxyde à caractère photocatalytique (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 467-477 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A photocatalyst like TiO2 may be introduced into a polymer to control the initiation process, to protect the photo-instable products, and to limit the oxidation to a surface phenomenon. In the case of aromatic polyurethanes, the quantum yields of photocatalytic oxidation are low as compared with the quantum yields of direct photooxidation. Photoactive pigments behave as stabilisers for the oxidation pathway. On the other hand, the photocatalyst acts as a screen for the Fries photorearrangement products and inhibits their photooxidation. Yellowing of polyurethanes is partly due to the photoinduced oxidation and partly to the Fires photorearrangement products. It is shown that in the presence of photoactive pigments the yellowing of polyurethanes due to Fires photorearrangement is the most determental process.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850305
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  • 384
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    Solution behaviour of polyacrylamides in 0,12 M NaClNCL Communication No. 3324. (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 549-557 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Seven unfractionated samples of polyacrylamide have been investigated in 0,12 M NaCl by viscosity, osmotic pressure, and light scattering techniques. Viscosity-molecular weight and 〈,s2〉w-M̄w relationships have been established and the unperturbed dimensions were estimated from the Stockmayer-Fixman relationship.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850313
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  • 385
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    Les effets thermiques associés à la transition vetreuse de films de poly(téearéphatalate d'éthylène) (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 601-613 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Differential scanning calorimetry and thermomechanical analysis are used for examining the thermal behaviour of amorphous poly(ethylene terephthalate) films in the glass-transition range. By variation of the heating rate between 0,2 and 100 K. · min-1, it is possible to obtain either an exotherm associated with a shrinkage, or an endotherm, or both of these phenomena. It is found that very low heating rates not only give rise to a retardation mechanism but also to a molecular rearrangement.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850318
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  • 386
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    The spontaneous polymerization of methyl methacrylate, 7Part 6: cf.6.. External heavy atom effect on the initiationPart of the dissertation of J. L., Mainz 1982.Dedicated to Prof. H. J. Cantow on the occasion of his 60th birthday (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 587-600 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A dimeric biradical •M2• plays a central role in the initiation of the spontancous polymerization of methyl methacrylate (M1). Besides the initiation step by chain transfer reaction, a change of the multiplicity of ·M2· seems to be of importance. Evidence is given by heavy atoms in the solvent or in an inert gas atmosphere, leading to an acceleration of the overall polymerization rate. The observed effect is related to the atomic number of the respective heavy atom. Measurements of the temperature dependence of the effect for carbon tetrachloride show that  -  as expected  -  no activation energy is needed for this reaction step. The results are summarized in a reaction scheme for the initiation mechanism of the spontaneous polymerization of methyl methacrylate.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850317
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  • 387
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    Functional monomers and polymers, 115Part 114: Y. Suda, Y. Inaki, K. Takemoto, Nucl. Acids Res., Suppl. 12, 169 (1983).. Permeability of hydrogel membranes consisting of copolymers containing pendant nucleic acid basesDedicated to Professor O. Wichterle on the occasion of his 70th birthday. (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 647-654 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hydrogel membranes consisting of copolymers from 2-hydroxyethyl methacrylate (1a) and vinyl monomers (1b, 2b, 1c, 2c) containing nucleic acid bases such as adenine and uracil, were prepared by casting technique. The permeability measurement of these membranes for adenine and uracil revealed a selective transport which depends on the copolymer composition of the membranes and the permeation conditions. Transport of adenine based on the difference of proton concentration was also observed. The specific interaction between complementary nucleic acid bases seems to play an important role in the permeation behavior.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850404
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  • 388
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    Polymer-linked acycloguanosine (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 687-695 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymer-linked 9-(2-hydroxyethoxymethyl)guanine (1) (acycloguanosine, acyclovir®) was prepared. Condensation of 1 with succinic anhydride gave in 77% yield 2-(9-guanylmethoxy)-ethyl hydrogen succinate (2), which was coupled through its carboxylic group either to poly(L-lysine) (M̄r = 55000) or to N-(6-aminohexyl)carbamoylmethylated dextran T80 to yield the polymers 3 and 4 (ligand concentrations in 3: 30 - 48 μmol of 2/g, in 4: 100 - 171 μmol of 2/g). From both polymers the antiviral 1 could be released by controlled saponification; the rate of drug delivery was found to be a function of pH and temperature. The polymeric carrier system 3 was degraded by endo-dextranase, and the carrier system 4 by trypsin, yielding low-molecular-weight derivatives of the pharmacon.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850407
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  • 389
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    Segmented block copolymer models of uniform chain length and defined structure, 1. Synthesis and characterizationDedicated to Prof. H. J. Cantow on his 60th birthday (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1335-1360 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Segmented block copolymer models of defined structure with molecular weights up to ca. 4000 were synthesized by specific condensation of monofunctional derivatives of oligo condensation products of 4,4′-isopropylidenediphenol (Bisphenol A) with terephthalic acid and oligomethylenes of uniform chain length. The oligo(arylester) blocks were prepared by stepwise addition of oxyterephthaloyloxy-1,4-phenyleneisopropylidene-1,4-phenylene units using a suitable protection and activation scheme. Similarly, oligo(arylester)s containing isophthaloyl and phthaloyl units were obtained. Telechelic oligomethylene segments were prepared analogously by combining functional derivatives of decane. All compounds were characterized by chemical, spectroscopic, and chromatographic methods.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850707
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  • 390
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    Caractérisation texturale par thermoporométrie, à l'état gonflé par l'eau, de résines échangeuses d'anions (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1105-1116 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoporometry is used to determine the size and the volume of the cavities of anion exchange resins swollen in water. The conditions of the application of thermoporometry are different of those met with non-functionalised resins. An important fraction of the water remains bond to the polymer and does not change its state when cooling. Nevertheless, it is possible to deduce from the freezing of the non-bound water the geometrical characteristics of the cavities of the resin which determine the fluid inside circulation. In most cases it is possible to confirm the pore size distribution by nitrogen adsorption and mercury porosimetry on resins partly swollen with water.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850604
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  • 391
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    Functional polymers and sequential copolymers by phase transfer catalysis, 2Part 1, cf.11.. Synthesis and characterization of aromatic poly(ether-sulfone)s containing vinylbenzyl and ethynylbenzyl chain endsPublication delayed upon author's request. (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1867-1880 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple method for the synthesis of α,ω-bis(vinylbenzyl) aromatic poly(ether-sulfone)s (2) and their transformation into α,ω-bis(ethynylbenzyl) aromatic poly(ether-sulfone)s (4) is presented. This method involves a fast and quantitative Williamson etherification of the α,ω-bis(hydroxyphenyl)polysulfone with a mixture of p- and m-chloromethylstyrenes in the presence of tetrabutylammonium hydrogen sulfate as phase transfer catalyst, a subsequent bromination, and then a dehydrobromination with potassium tert-butoxide. The DSC study of the thermal curing of these α,ω-bis(vinylbenzyl)polysulfones and α,ω-bis(ethynylbenzyl)polysulfones demonstrates high thermal reactivity for this new class of styrene-terminated oligomers.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850909
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  • 392
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    Polyurethanes containing binaphthyl groups (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1915-1920 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyurethanes containing binaphthyl groups were synthesized by reaction of diisocyanates - 4,4'-diphenylmethane diisocyanate (MDI), 2,4-toluylene diisocyanate (TDI) and hexamethylene diisocyanate (HDI) - with 2,2'-(1,1'-binaphthyl-4,4'-ylenedioxy)diethanol (3). The polyurethane obtained from 3 with MDI has an intrinsic viscosity [η]90DMSO90°C of 0,14 dl · g-1 and a melting point of 244 - 260°C, that from 3 with TDI has an [η]90°CDMSO of 0,12 dl · g-1 and a melting point of 181 - 191°C, and that from 3 with HDI has an [η]90°CDMSO of 0,11 dl · g-1 and a melting point of 222 - 241°C. These polymers were found to be crystalline. Segmented polyurethanes (SPU) from 3 with prepolymers of poly(tetramethylene glycol) (PTG), (M = 1079) and MDI or HDI (mole ratio PTG:MDI (or HDI) = 1:2) were also synthesized. The SPU from MDI has an intrinsic viscosity [η]90°CDMSO of 0,56 dl · g-1 and a melting point of 260-275°C, and that from HDI has an [η]90°CDMSO of 0,50 dl · g-1 and a melting point of 231 - 253°C. These polymers show slight crystallinity.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850913
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  • 393
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    Random coil configurations of poly(diethylene glycol isophthalate)Systematic nomenclature: poly(oxyethyleoxyethyleneoxyisophthaloyl).. Capability of model network formation (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1943-1952 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Values of the mean-square dipole moment 〈μ2〉 of poly(diethylene glycol isophthalate) were determined as a function of temperature by means of dielectric experiments carried out on solutions of the polymer in benzene. The value of the dipole moment ratio 〈μ2〉/(nm2), where nm2 is the mean-square dipole moment of the chains in the idealization that all of the skeletal bonds are freely jointed, is 0,697 at 30°C. Trifunctional model networks were prepared by endlinking hydroxyl-terminated chains with an aromatic triisocyanate. From thermoleastic experiments performed on the networks over the temperature range 20-80°C, it was found that the value of the temperature coefficient of the unperturbed dimensions 103 d In 〈r2〉0/dT amounts to 1,05 ± 0,17 K-1. The dipole moments and the temperature coefficients of both the dipole moments and the unperturbed dimensions were critically interpreted in terms of the Ratational Isomeric State (RIS) model. Stress-strain experiments were also performed at 70°C on swollen and unswollen networks. The analysis of the isotherms suggests that the chemical crosslinks are not sufficient to account for the high modulus exhibited by the networks.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850916
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  • 394
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    Spectroscopic test of the pressure effect on complexes of poly(N-vinylcarbazole) and derivatives with tetracyanoethylene (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1991-1999 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The absorption spectra of the complexes of tetracyanoethylene with poly(N-vinylcarbazole), poly(N-vinyl-3-chlorocarbazole), and poly(N-vinyl-3,6-dichlorocarbazole) were investigated in the visible range as a function of the pressure. The degree of complexation expressed by the equilibrium constant, the oscillator strength, and the excitation energy were determined. A significant increase of the oscillator strength was observed, when the pressure increases, this being in agreement with Mulliken's theory. With increasing pressure the absorption maximum of the CT complex was shifted towards the infra-red. Two peaks were found as a consequence of a splitting of the absorption band under the influence of pressure. This effect is discussed in terms of the existence of orientational isomers. An influence of the substituents (chlorine) in 3-and 3,6-positions of carbazole on the spectral properties of the complexes was found.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850919
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  • 395
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    Speckle patterns in small angle light scattering: A random phase screen approach (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2021-2031 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The basic features of scattering are shared by a number of closely related scatterer systems. The most elementary model for these systems in the random phase screen (RPS). In this article, predictions of the RPS theory are compared with the experimental data obtained by analysing scattered light speackle patterns from a film made of a semicrystalline polymer. On the basis of results obtained, it is possible (a) to classify speckle types depending on the illuminating conditions, (b) to measure speckle “smoothing” by determining the contrast of speckle intensity fluctuations, (c) to illustrate the relation between object and speckle movements in different geometries for simple types of sample movement (rotation, linear continuous translation and step-wise translation). The experimental data tend to confirm the validity of RPS theory in the case of polymer films. It is indicated that under certain conditions the statistical, temporal and spatial coherence properties of the scattered light are sensitive to the detailed internal structure of the scattering medium.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850922
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  • 396
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    Metalloesters, 11Part 10: cf. Makromol. Chem. 184, 2021 (1983).. “Disproportionation” of living (lithiated) oligomers of methyl methacrlylate (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1819-1826 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The decomposition reactions of the lithiated dimer, trimer, and tetramer of methyl methacrylate (MMA) in THF at 25°C were investigated. The decomposition of the lithiated dimer proceeds via depolymerization to lithiated monomer and MMA, addition of MMA to residual lithiated dimer, resulting the trimer (“disproportionation” of the dimer), and subsequent autocondensation of the products. The lithiated trimer almost exclusively undergoes cyclo-autocondensation, whereas for the lithiated tetramer both reactions proceed simultaneously to a remarkable degree. It is shown that the relative rate of autocondensation, which is highly dependent on the degree of polymerization of the oligomer, controls the distribution of products formed. The results indicated that the depolymerization of living PMMA is an important factor even at room temperature, potentially affecting the MWD of the polymers.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850904
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  • 397
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    Carboxyl-terminated poly(vinyl alcohol). Chain transfer of methyl propionate to vinyl acetate (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2299-2304 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(vinyl acetate) was prepared at 60°C with benzoyl peroxide by using methyl[carbonyl-14C] propionate as chain transfer agent and solvent. The resulting polymer was hydrolysed to poly(vinyl alcohol) (PVAL) having carboxyl end groups and the average number of carboxyl groups per chain was unambiguously determined by comparing the activity of the polymer to that of the methyl propionate. An average density of 1,5 carboxyl groups per chain was found for poly(vinyl alcohol) prepared from poly(vinyl acetate) of DP 80 - 90. Other methods of end group analysis for carboxyl groups in PVAL are discussed.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/macp.1984.021851107
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  • 398
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    Synthesis and investigation of the properties of polymers containing dicarbaundecaborate (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2313-2318 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymides containing dicarbundecaborate moieties (1) are formed by nucleophilic degradation of polyamides containing 1,7-dicarba-closo-dodecaborane(12) (m-carborane) moieties in the polymeric chain. The formation of polyamides 1 is accompained by decomposition of the polymeric chain. Potassium cations in the dicarbundecaborate moieties were shown to be easily replaced by protons. The structure of polymers containing exclusively dicarbaundecaborate units (2) was investigated by IR and 1H NMR spectroscopy. Some chemical and physico-chemical properties of these polyamides were studied.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021851109
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  • 399
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    Untersuchungen zu Modifikationen von Polyamid-6 und Polyamid-4 mit eingelagerten Alkalihalogeniden (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 1953-1977 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyamide-6 (PA-6) and polyamide-4 (PA-4) doped with alkali halides were investigated by X-ray diffraction, thermal analysis, infrared and far infrared spectroscopy at various temperatures (10 K - 300 K). The solubility of the alkali halides in PA-4 is better than in PA-6. Small ions are molecularly dispersed in PA-6 and PA-4. Alkali ions are coordinated to the oxygen, halide ions to the nitrogen of the amide group. The degree of crystallinity of the polyamides depends on the concentration of the alkali halides and the ion radii. Alkali halides stabilize modifications of the polyamides with not fully extended chains. In polyamides crystallized from the melt some alkali halides stabilized the γ-modification or similar structures. The modification is nearly independent of the alkali halide concentration and will not be destroyed by washing out the alkali halides. If the polyamides are crystallized from formic acid, alkali halides promote a pleated sheet structure with antiparallel chains. The factor group of the layer is D2, indicated by a low temperature splitting of the B2 vibration modes.
    Additional Material: 14 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1984.021850917
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  • 400
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    Studies of crosslinked poly(N-vinyl-2-pyrrolidone) by calorimetry and by NMR (1984)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 185 (1984), S. 2011-2019 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Aqueous solutions of poly(N-vinyl-2-pyrrolidone) are converted to gels by reaction with potassium peroxydisulfate K2S2O8. The degree of crosslinking in the gel fractions depends on the amount of persulfate used. The degree of crosslinking is related to the amount of non-freezing bound water in the gels by means of differential scanning calorimetry in the temperature range from -50°C to + 170°C. The chemical nature of the bonds formed during gelation is studied by 1H and 13C NMR Spectroscopy and by swelling tests. NMR measurements point to the formation of aliphatic sidechains as well as crosslinks in the gelation. The swelling tests give low values for the number of crosslinks, hence the formation of branched chains strongly influences the properties of the gels. In contrast to what was expected no carboxyl groups are found in the gels.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1984.021850921
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