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  • Articles  (8,168)
  • Chemistry  (8,168)
  • 1980-1984  (8,168)
  • 1935-1939
  • Physics  (8,168)
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  • Articles  (8,168)
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  • 101
    Electronic Resource
    Electronic Resource
    Copolymers of 2-acrylamido-2-methylpropanesulfonic acid and aromatic vinyl compounds as potential media for photosensitized electron transfer reactions (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3135-3147 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In an expectation as potential media for photosensitized electron transfer reactions, polymers carrying both strong electrolytic and hydrophobic segments were prepared by the copolymerization of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and styrene. The AMPS segments were found to have a remarkable power to solubilize the hydrophobic segments into water, i.e., even a copolymer with a styrene mole fraction of 0,72 is still soluble in water. Salt effect on the reduced viscosity, broadening of NMR spectra in D2O, and enhanced excimer fluorescence of styryl groups in aqueous solution indicated a pronounced hydrophobic interaction of a number of styryl groups along the chain in the copolymer with high styrene content. 8-Anilinonaphthalene-1-sulfonic acid, 1,6-diphenyl-1,3,5-hexatriene, and a cyanine dye were used as fluorescent probes for the hydrophobic microdomains. The results suggested that the microdomains are highly hydrophobic in nature but less capable to solubilize the fluorescent probes than the surfactant micelles. An electron microscopic image of the copolymer was also discussed as a supporting evidence for the presence of microdomains.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021821120
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  • 102
    Electronic Resource
    Electronic Resource
    Internal mobility of PMMA in concentrated CDCl3 solutions, 1. 1H NMR spectra (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3169-3176 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of the second moment and analysis of the derivative shape of 1H NMR spectra of PMMA have shown that in CDCl3 solutions containing 60% (w/w) or more of polymer, the internal mobility of PMMA is similar to the mobility of the pure polymer. The main chain is rigid on the NMR scale, and only CH3 groups are mobile. The motion of CH2 groups, representing the segmental mobility of the backbone chain, becomes appreciable on the NMR scale at concentreations of 60-50%, depending on the temperature. Measurements of 1H MAR-NMR spectra of solutions containing 30% or more of polymer indicate spatial anisotropy of internal motions of PMMA. This spatial anisotropy is probably due to intermolecular interactions of ester groups, similarly as in the gels of the PMMA stereocomplex.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021821123
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  • 103
    Electronic Resource
    Electronic Resource
    Die molekulargewichtsverteilung bei der kontinuierlichen anionischen polymerisationHerrn Professor Dr. Dres. h. c. G. V. Schulz mit den besten Wünschen zum 75. Geburtstag gewidmet (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3207-3221 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Equations are given for the continuous anionic polymerization in a tubular reactor which describe the resulting molecular weight distribution as a function of the size of the mixing zone and of the concentration of chain terminating impurities in the solution of the monomer. Polymerization of styrene and of butyl methacrylate was conducted with different initiator concentrations, and the size of that part of the reactor where backmixing occurs was estimated from the molecular non-uniformity of the polymers, whereas the degree of polymerization allows the determination of the concentration of the impurity. This latter quantity apparently increases with initiator concentration in the case of methacrylate polymerization and therefore suggests a reaction of the initiator with the ester group to occur. The shape of the molecular weight distribution indicates termination of the growing methacrylate chains, possibly by reaction of living chain ends with ester groups.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021821127
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  • 104
    Electronic Resource
    Electronic Resource
    Elementarprozesse löslicher ziegler-katalysatoren. Polymerisationskinetische analyse und mathematische modellierung im system Cp2TiPropylCl/AlEtCl2/ethylenHerrn Prof. Dr. Dr. h. c. Franz Patat zum 75. Geburtstag in Verehrung gewidmet (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3265-3278 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper deals with the kinetics of the polymerization of ethylene catalysed by the soluble Ziegler-catalyst Cp2TiPropylCl/AlEtCl2. By means of a special method it was possible to study the kinetics of the initial instationary homogeneous part of the polymerization. The dependences of the initial rates on the catalyst components prove that the polymerization active species is formed in two successive very dynamic equilibria. The primary complex equilibrium is entirely located on the right hand side, whereas the second equilibrium depends considerably on the ratio of the catalyst components and is shifted on the active species side only at very high Al/Ti ratios. Because of this location of the two successive equilibria the dependence of the polymerization velocity vp on the charged Al concentration (that is, the Al isotherm) has to show a sigmoidal curve course in the inital part, which experimentally is confirmed exactly. Finally, this extensive kinetical analysis leads to the complete reaction scheme of the polyreaction and by mathematical modelling to the quantitative calculation and description of the experimental curves and dependences (e.g., Al-isotherm).
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021821131
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  • 105
    Electronic Resource
    Electronic Resource
    Thermomechanical analysis of linear aromatic polyesters (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3323-3330 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermomechanical properties of linear aromatic polyesters, studied using thermomechanical analysis techniques, have been related to the chemical structure and methylene chain length. An increase in the number of methylene groups, the use of an asymmetric diacid, or random copolymerization of the repeating units of these polyesters, resulted in a lower linear thermal expansion coefficient α, a lower Vicat softening temperature Ts, a lower heat deflection temperature Td, and a lower glass transition temperature Tg. With longer methylene sequence lengths, the influence of the methylene groups on the thermomechanical properties is predominant, the data are closer together. The values are generally highest for the terephthalate series and lowest for the copolymer series. Glass transition temperatures calculated from group contributions and measured experimentally agreed. The deflection temperatures approximated the glass transition temperatures and the Vicat softening points the melting temperatures.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021821135
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  • 106
    Electronic Resource
    Electronic Resource
    Phase distribution chromatography (PDC) as a method for the investigation of polymers in solution, 2Part 1: Cf.1.. Flow-equilibrium (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2845-2861 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamical region of the measured calibration curves is investigated using the results of the theory published previously. The kinetic constants of the flow-equilibrium are calculated from the measurements according to two different models for a spontaneous polymer diffusion of the transported P-mer from sol into gel of the Phase Distribution Chromatography (PDC)-column. The corresponding lateral concentration profiles in the gel are found by analytical integration of Fick's second law under the corresponding boundaries. An energetic model of this flow-equilibrium is stated, giving the activation enthalpy and -entropy of the rediffusion of the polymer from gel into sol after some retardation time in the gel. The influence of the gel mass of the column on its resolution is briefly investigated. Since the measurements show that the resolution of the PDC-column vanishes in the vicinity of the theta point, spreading phenomena in the column can be investigated by means of analysis of the corresponding PDC elution curves. The results give a basis for the numerical computation of the molecular weight distribution of narrowly distributed polystyrenes from PDC elution curves at sufficiently low column temperatures. The PDC-separation effect is opposite to that of gel permeation chromatography (GPC).
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021821029
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  • 107
    Electronic Resource
    Electronic Resource
    Lösungseigenschaften methyl- und chlorsubstituierter Bisphenol-A-PolycarbonateHerrn Prof. Dr. Grünewald zum 60. Geburtstag gewidmet (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2873-2879 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solution properties of dilute polymer solutions are studied for polycarbonates from 3,3′,5,5′-tetramethylbisphenol A, from 3,3′-dimethylbisphenol A, from 3,5-dimethylbisphenol A, and from 3,3′,5,5′-tetrachlorobisphenol A in regard to the influences of the different methyl and chloro substitutions. The Mark-Houwink relationships are established in dichloromethane at 25°C. The unperturbed dimensions, evaluated from viscosity data using the Burchard-Stockmayer-Fixman method, are compared with those for bisphenol A polycarbonate. The unperturbed end-to-end distances are increased by the methyl and chloro substituents. The flexibility factors, calculated on the basis of the unperturbed dimensions and the dimensions of the freely rotating chain, indicate a greater rigidity of the polymer chain of the methyl and chloro substituted polycarbonates.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021821031
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  • 108
    Electronic Resource
    Electronic Resource
    Polymers containing enzymatically degradable bonds, 4Part 3: cf.3. Preliminary experiments in vivo (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2941-2949 
    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 N-(2-hydroxypropyl)methacrylamide containing oligopeptidic sequences either in side chains or as part of crosslinks were prepared. These polymers were applied intravenously to rats, and spectrophotometric analysis (oligopeptidic side chains) or gel permeation chromatography of urine (oligopeptidic crosslinks) have shown that both types of polymers are cleavable in vivo.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021821102
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  • 109
    Electronic Resource
    Electronic Resource
    Uncatalysed phenol-formaldehyde reactions. A convenient synthesis of all-ortho novolac resinsCf.:1 (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2973-2979 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The uncatalysed reaction between phenol and paraformaldehyde in aprotic nonpolar media at 170-220°C provides an efficient inexpensive route to novolac resins with almost all of the methylene-linkages in ortho-ortho′ sequence. The role played by the solvent is shown to be determinant in the ortho-specific insertion of methylene-bridges between the phenolic units.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021821105
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  • 110
    Electronic Resource
    Electronic Resource
    The structure of poly(N-vinylcarbazole) obtained with cationic initiators and electron acceptors as catalysts (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3003-3015 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(N-vinylcarbazole)s, [poly(l-(N-carbazolyl)ethylene)s], (PVCz's) were prepared under various polymerization conditions. The stereoregularities were estimated by means of 13C NMR spectroscopy. Although the stereoregularity of the polymers obtained by BF3O(C2H5)2 was hardly changed by the polymerization temperature, it changed with the solvent polarity from an isotactic-rich configuration in toluene and CH2Cl2 to a syndiotactic-rich configuration in nitrobenzene. The 13C NMR spectra of the polymers obtained by organic electron acceptors, support the conclusion that the polymerization by tetracyanoethylene, p-bromanil, 2,3-dichloro-5,6-dicyano-p-benzoquinone, and tetrachlorophthalic anhydride proceed by a cationic mechanism. In the polymerization of N-vinylcarbazole (VCz) with maleic anhydride as an electron acceptor, a small amount of copolymer was obtained together with the homopolymer of VCz. Although the structure of the homopolymers is the same as that of the radically obtained polymer, it is considered that the polymer is formed by a cationic mechanism. The polymerizations of VCz by inorganic compounds, such as ferric nitrate, cupric nitrate, cupric bromide, etc., as catalysts are cationic.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021821109
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  • 111
    Electronic Resource
    Electronic Resource
    Etude de radicaux libres forméas par irradiation ultraviolette de l'amidon: Application aux réctions de photodégradation et de photogreffage (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3053-3068 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: General investigations of radical processes in starch were carried out. ESR experiments showed that UV irradiation of starch, both in photosensitized and unphotosensitized experiments, results in chain scission and radical generation on the glucosidic ring. It was shown that benzophenone, deoxybenzoin and derivatives (2a-d) are efficient sensitizers. The ESR spectra were interpreted by assuming superposition of three signals; they were ascribed to radicals formed by chain scission and hydrogen abstraction. In addition photodegradation processes of starch in the presence and absence of photosensitizers were investigated. The amount of chain scissions was followed under various experimental conditions and appeared as a function of the initiator. Moreover, oxygen was shown to enhance the yield of chain scissions: this was explained through the formation of peroxide functions at C1-position. UV light induced grafting of a vinyl monomer onto starch was also investigated. It appeared that chemical grafting can easily be achieved through a radical reaction. Moreover, the percentages of grafting and degradation were strongly dependent on the photoinitiator. The whole results gave the possibility to select an efficient initiator of the grafting reaction. In the case of methyl methacrylate, α,α-dimethoxydeoxybenzoin (2a) appears to be the most efficient initiator. However, previous works as well as the present work suggest that the grafting efficiency is strongly dependent on the three components: substrate, monomer, and initiator.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021821113
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  • 112
    Electronic Resource
    Electronic Resource
    Electric dipole moment of ethylcellulose, in 1,4-dioxane and in benzene (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3109-3117 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The electric dipole moments per repeating unit of ethylcellulose (EC) of various molecular weights were determined by dielectric measurements at 1 kHz (μL) and at 1 MHz (apparent moment, μH) in 1,4-dioxane and benzene. The numerical values were μL = 5,23 D (= 17,45.10-30 C·m) and μH + 2,72 D (= 9,07.10-30 C·m) for 1,4-dioxane, and μL = 4,81 D (= 16,04.10-30 C·m) and μH = 2,42 D (= 8,07.10-30 C·m) for benzene, respectively. μL and μH were almost independent of the molecular weight in both solutions. The persistence dipole moment μq was estimated to be 13,6 D (= 45,36.10-30 C·m) in 1,4-dioxane, and 13,4 D (= 44,70.10-30 C·m) in benzene, respectively, and the flexibility of the EC chain was discussed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021821117
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  • 113
    Electronic Resource
    Electronic Resource
    Hochmolekulare makrocyclische polycarbonate (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 111-124 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Interfacial condensation polymerization of bischloroformates of bisphenol A with bisphenol A results in the formation of cyclic aromatic polycarbonates of high molecular weight. Products made by this technique show a significant reduction (up to 95%) in their end group content. Also, in comparison to molecular weights determined by light scattering, these products show markedly lower molecular weights by solution viscocity measurements and by applying the Mark-Houwink equation for linear polycarbonates. The existence of high molecular weight cyclic polycarbonates is confirmed by a controlled saponification reaction using piperidine as a basic compound. The saponification reaction causes nearly no change in the number average molecular weight of the polymer and causes an increase in the number of end groups of up to 2 end groups per molecule. The observed increase in the intrinsic viscosity data is similar to what would be expected from linear polycarbonates. It is shown that cyclic polycarbonates with molecular weights exceeding 100 000 are easily obtained.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1980.021810111
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  • 114
    Electronic Resource
    Electronic Resource
    Die thermische polymerisation von methylmethacrylat, 2.Teil 1: cf.1. Bildung des ungesättigten dimerenHerrn Professor Dr. H. Pommer zum sechzigsten Geburtstag gewidmet (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 131-147 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The spontaneous thermal polymerization of methyl methacrylate (MMA) is accompanied by the production of serveral oligomers among which a linear unsaturated dimer H-1 (dimethyl 1-hexene-2,5-dicarboxylate) is predominant. The reaction kinetics of this dimer formation was investigated in bulk and in solution. The temperature dependence of the second order dimerization constant was determined as \documentclass{article}\pagestyle{empty}\begin{document}$$ \log _{\rm e} k_{{\rm H} - 1} = 13,11 - \frac{{107,2{\rm }{{{\rm kJ}} \mathord{\left/ {\vphantom {{{\rm kJ}} {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}}}}{{RT}} $$\end{document} Reaction mechanisms for the thermal dimer formation of MMA are discussed.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1980.021810113
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  • 115
    Electronic Resource
    Electronic Resource
    Preparation and 13C NMR spectra of model compounds for poly(4-bromostyrene) (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 125-130 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The preparations of 2,4-bis(4-bromophenyl)pentane (1b) and 2,4,6-tris(4-bromophenyl)heptane (2b) are described. The study of the different isomers of 1b and 2b by 13C NMR allows a comparison of the various configurational sequences of these compounds in terms of their chemical shifts. Methyl, methylene, and aromatic C1 carbons of 1b and 2b could be deduced from the values obtained from corresponding polystyrene model compounds by a mere translation. From the aromatic C1 chemical shifts it was possible to propose an assignment of the corresponding triads of poly(4-bromostyrene).
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1980.021810112
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  • 116
    Electronic Resource
    Electronic Resource
    Hot drawing of surface growth polyethylene fibers, 2Part 1: cf.2. Effect of drawing temperature and elongational viscosity (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3351-3359 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A distinct improvement of the tensile properties of “surface growth” polyethylene fibers can be realised by drawing at elevated temperatures. The optimal drawing temperatures were found in the range of 120-150°C. Drawing in the hexagonal phase above 150°C does not lead to an increase of strength. Elongational viscosity measurements revealed extremely high values in the order of 1011-1012 Poise. Activation energies between 75-95 kJ/mol were determined from the temperature dependence of elongational viscosity. The observed drawing behaviour is discussed in relation to the morphological changes that occur during drawing.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021821138
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  • 117
    Electronic Resource
    Electronic Resource
    Helix-coil transition in polypeptides having linear alkyl side-chain and ester group, and some conformational aspects observed by 13C NMR (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 165-175 
    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 has been used to study the helix-coil transition induced in polypeptides by trifluoroacetic acid. An attempt is made to separate the influences of conformational change and direct solvent interaction. For poly(γ-methyl-L-glutamate), interactions between trifluoroacetic acid and the ester group of the side chain occur in the helical region. Poly(L-norvaline) and poly(L-norleucine) are in the form of “partially distorted helical conformation”. Conformational change and the interaction between trifluoroacetic acid and the peptide group which accompany the helix-coil transition, affect the chemical shift difference up to Cδ or Cβ of poly(L-norvaline) and poly(L-norleucine), On the contrary, in the case of polyglutamates and polyaspartate, these effects are minor for the carbons in the ester portion. The chemical shift differences of these polypeptides can be well interpreted qualitatively by the results for some butyrates, poly(L-norvaline), and poly(L-norleucine).
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1980.021810115
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  • 118
    Electronic Resource
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    Induced 13C shifts by coil-supporting solvents observed in oligopeptides as model compounds of polypeptides (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 177-191 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The origin of the chemical shift differences of carbons in polypeptides which accompany the helix-coil transition has been investigated by using oligopeptides, benzyloxycarbonyl-γ-ethyl-L-glutamyl-diethyl-L-glutamate and benzyloxycarbonyl-di-(γ-ethyl-L-glutamyl)-diethyl-L-glutamate, as models of the backbone of polypeptides. Structures of aggregates in deuterated chloroform were proposed for these oligopeptides on the basis of concentration dependence and temperature dependence of the chemical shifts of protons and carbons, and spin-lattice relaxation times. Antiparallel and/or parallel “in-register” structures for extended forms and “out-of-register” network of extended forms are coexisting in deuterated chloroform solution for these oligopeptides. From the shift for the carbons of the oligopeptides induced by organic acids, it was in ferred that down-field shifts are induced at α and amide carbons in polypeptides by organic acids. By comparing the induced shift of the carbons in the peptides with the chemical shift differences of the carbons in polypeptides which accompany the helix-coil transitions, it was found that the conformational changes play a predominant role in the origin of the chemical shift differences of the carbons in polypeptides which accompany the helix-coil transitions, it was found that the conformational changes play a predominnant role in the orgin of the chemical shift differences of amide, α, β, and γ carbons in polypeptides.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1980.021810116
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  • 119
    Electronic Resource
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    Poly(L-lysine)/sulfated poly(vinyl alcohol)/acridine orange complex (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 193-199 
    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 clarify the arrangement of sulfated poly(vinyl alcohol) (PVS) chains about the α-helical poly(L-lysine) (PLL) chain in the previously reported complexes of PLL/46 mole-% sulfated poly(vinyl alcohol) (PVS-46) and PLL/PVS-95, induced circular dichroism was studied on PLL/PVS/acridine orange (AO) complexes in acidic aqueous solution. A positive ellipticity, [θ], of ca. 3 400 deg·cm2·dmol-1 at 465 am and small negative values of [θ] at 435 and 510 nm indicated a right-handed super helical arrangement of AO molecules about the right-handed α-helix of PLL, where PVS chains were intercalated. The amount of AO molecules responsible for the induced CD was estimated as low as a few mole-%. Taking into consideration the arrangement of ε-amino groups of the right-handed α-helical PLL and the distance among the neighboring ε-amino groups on the radial projection of the helix, the PVS chain segments could be arranged both in the right-handed and in the left-handed superhelices about the right-handed α-helix of PLL. In cases of the PLL/PVS-25/AO and PLL/PVS-30/AO complexes, no induced CD and a quite weak CD were obtained, resp., being consistent with random coil conformation of PLL in the PLL/PVS-25 and PLL/PVS-30 complexes mentioned previously.
    Additional Material: 4 Ill.
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    Characterisation of poly(acrylamide) in solution (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 227-240 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using a set of laboratory poly(acrylamide) samples in the molecular weight region M̄w = 5.105 to M̄w = 6.106 the following relations have been established, the polymer concentration c given in g/cm3: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {[\eta ] = 4,9 \cdot 10^{ - 3} \bar M_{\rm w}^{{\rm 0,8}} } \hfill & {\rm,} \hfill & {{\rm solvent: H}_{\rm 2} {\rm O, temp}{\rm .: 298 K}} \hfill \\ {[\eta ] = 7,19 \cdot 10^{ - 3} \bar M_{\rm w}^{{\rm 0,77}} } \hfill & {\rm,} \hfill & {{\rm solvent: 0,5 M aqueous NaCl, temp}{\rm .: 298 K}} \hfill \\ {[\eta ] = 1,36 \cdot 10^{ - 1} \bar M_{\rm w}^{{\rm 0,54}} } \hfill & {\rm,} \hfill & {{\rm solvent: ethylene glycol, temp}{\rm .: 298 K}} \hfill \\ {s_0 = 0,9 \cdot 10^{ - 1} \bar M_{\rm w}^{{\rm 0,32}} } \hfill & {\rm,} \hfill & {{\rm solvent: 0,5 M aqueous NaCl, temp}{\rm .: 293 K}} \hfill \\ \end{array} $$\end{document}([η], intrinsic viscosity; s0, sedimentation constant) Mainly based on light scattering experiments a more detailed description on molecular dimensions and solution structure of PAAm/H2O and PAAm/ethylene glycol systems is given. In both systems the relation a = 3v - 1 (a and v being the exponents of the intrinsic viscosity  -  and root-means-square end-to-end distance  -  molecular weight functions) holds.
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    Effect of UV light on the system styrene/maleic anhydride at -196°C (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 255-260 
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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 effect of UV light (λ 〉 300 nm) on the system styrene/maleic anhydride/solvent (acetone or chloroform) in the presence and/or absence of the alternating styrene/maleic anhydride copolymer was studied by the ESR method at -196°C. It was found that the concentration of paramagnetic species increased with the time of irradiation. The intensity of the ESR spectra at -196°C did not change when the light was cut off. By analysis of the ESR spectra of the systems studied the methyl (aH = 2,3 mT), dichloromethyl (aH = 1,66 mT), and acetyl (aH = 0,52 mT) radicals as well as the radicals A and D (aHα = 2,25 mT, aHβ = 3,19 mT) and (aHβ = 1,1 mT), respectively, were identified.
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    Untersuchungen zur stereospezifischen pfropfung von butadien auf chloriertes polycyclopentadien (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 267-276 
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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: Products with 〉90% of 1,4-cis-units in the grafted chains are obtained by employing suitable concentrations of cobalt complexes as an initiator component in the grafting of butadiene onto chlorinated polycyclopentadiene. Grafting efficiencies 〉90% can be achieved. In contrast to grafting without using cobalt complexes the reaction rate is faster. Suitable solvents are chlorobenzene, 1,2-dichloroethane, or dichloromethane. Grafting efficiency, degree of grafting, and the molecular weights of the grafted chains are obtained by selective extraction of the grafts with pentane. The results suggest a cationic-coordinative mechanism, in most cases accompanied by a “pure” cationic grafting.
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  • 123
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    The copolymerization of methacrylaldehyde with hydrophilic monomers (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 367-372 
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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: Copolymers of methacrylaldehyde with hydrophilic monomers  -  2-hydroxyethyl methacrylate, 5-hydroxy-3-oxapentyl methacrylate, 8-hydroxy-3,6-dioxaoctyl methacrylate, N-ethylmethacrylamide, N,N-diethylacrylamide, and N,N-diethylmethacrylamide  -  were prepared by solution polymerization in N,N-dimethylformamide initiated with 2,2′-azodiisobutyronitrile. In the copolymer of methacrylaldehyde (1) with 2-hydroxyethyl methacrylate (2) (r1 = 0,77, r2 = 0,36) and in the copolymer of methacrylaldehyde with N,N-diethylacrylamide (r1 = 3,79, r2 = 0,14) the content of CH=O groups corresponds to that ot methacrylaldehyde units in the triads comonomer  -  methacrylaldehyde  -  comonomer; in the copolymer of methacrylaldehyde with N-ethylmethacrylamide (r1 = 4,07, r2 = 0,14) both comonomers react with each other and the content of CH=O groups is very low, while in the copolymer of methacrylaldehyde with 5-hydroxy-3-oxapentyl methacrylate (r1 = 1,48, r2 = 0,34) the majority of methacrylaldehyde units contain an unreacted CH=O group.
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    Dependence of non-Newtonian flow properties of polystyrene solutions on solvent viscosity (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 399-407 
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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: Steady shear viscosities were measured over a range of shear rates from lower to upper-Newtonian flow region for solutions of polystyrene in the high-viscosity solvent tricresyl phosphate at three different temperatures. The influence of solvent viscosity on the non-Newtonian flow property was studied and compared with the results obtained previously by use of a lowviscosity solvent with similar solvent power for polystyrene as tricresyl phosphate. For the moderately concentrated solutions, the non-Newtonian viscosity could be explained by Graessley's entanglement viscosity theory modified by a frictional viscosity. The result shows that only the frictional viscosity is affected by variation of solvent viscosity. As the entanglement viscosity decreases with increasing shear rate and is practically masked by the shear independent frictional viscosity, the flow appears as to be upper-Newtonian in spite of the difference in solvent viscosity. The lower critical concentration for entanglement was determined on the basis of a lower limit for the applicability of the modified Graessley theory. The values of the critical concentrations are independent of the magnitude of solvent viscosities.
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    Polymer-solvent interactions in mixed solvents, 1. Isotactic, syndiotactic and atactic poly(methacrylic acid) in water/2-chloroethanol mixtures (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 469-484 
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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 viscosimetric behaviour and the preferential solvation of syndiotactic, isotactic, and atactic poly(methacrylic acid), [poly(1-carboxy-1-methylethylene)] are studied in water/2-chloroethanol mixtures. The experimental results show that the preferential solvation of the polymer is strongly dependent on its local conformation. In the case of the syndiotactic sample, a close correlation has been established between the compact structure ↔ coil conformational transition and the variation of the preferential and absolute solvation of the polymer by 2-chloroethanol, asserting the importance of hydrophobic interactions in the stabilization of the compact structure. Experimental data concerning the isotactic sample suggest the existence of an “inverse compact structure” in 2-chloroethanol-rich mixtures.
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  • 126
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    Conformational change of poly(L-lysine) by formation of complexes with poly(styrene sulfonate) (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 497-506 
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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: Circular dichroic studies were made on the conformational change of poly(L-lysine) (PLL) by complex formation with sulfonated polystyrenes (PSS) as functions of pH, temperature and polymer compositions in comparison with the complexes of PLL with sulfated poly(vinyl alcohol) (PVS). The coil-to-helix transition of PLL by complex formation at neutral and acidic pHs, which took place in the PLL/PVS (with high degrees of sulfation) complexes, was prevented in the PLL/PSS complexes due to the less chain flexibility of PSS than PVS. Above pH 11, the α-helix of PLL was partially broken into random coil by complex formation with PSS. The drastic decrease in the solution viscosity by the complex formation revealed a large contraction of PSS chain and subsequently a large strain of the α-helical PLL chain so as to give the breakdown of the α-helix. This is denoted a strain-induced conformational change of PLL. It was found that the α-helix of PLL was thermally stabilized by the complex formation with PSS as in the case of PLL/PVS complexes. A β-to-α transition of PLL by the complex formation with PSS was also found, while the β-form was maintained in the PLL/PVS (with high degrees of sulfation) complexes.
    Additional Material: 3 Ill.
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    Über enzymanalog gebaute Polymere, 11.Teil 10: cf. 1. Bindungsstellen im Polymer mit unterschiedlicher Zahl der HaftgruppenProfessor Matthias Seefelder zum 60. Geburtstag gewidmet (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 531-544 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 4-Vinylphenylboronic esters 1 and 2 of L-1,2-propandiol (3a) resp. D-mannitol (4a) were polymerized under different conditions to macroporous, crosslinked copolymers. Afterwards the alcohols 3a resp. 4a were split off. The alcohols have thus been used to form chiral microcavities within the polymer, of which those prepared from 1 contain 1 and those from 2 contain 3 binding groups —B(OH)2. Binding sites with 2 binding groups have been investigated before. These polymers possessed capacity for the resolution of the racemate of the template used. The kinetics of the mass transfer within polymers with three binding groups per cavity is discussed in more detail. The chromatographic investigation of the binding ability at different pH-values of polymers from 2 for D-mannitol showed even in acidic media a pronounced binding through neutral esters 5, whereas in alcaline media a much stronger binding through basic esters 6 occurred.
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    Polymere 2,2,6,6,-Tetraalkylpiperidin-Derivate, 1. Tetra- und Pentaalkylpiperidin-Derivate von Polyacryl- und Polymethacrylestern, Polyacryl- und PolymethacrylamidenHerrn Prof. Dr. H. Batzer zum 60. Geburtstag gewidmet (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 595-633 
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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 number of tetra- and pentaalkylpiperidine derivatives of acrylic and methacrylic acid was synthesized, polymerized, and copolymerized with several comonomers as potential UV stabilizers. In addition, by oxidation of some of these polymers and of a copolymer with peroxy compounds, polymers were obtained containing pendant nitroxyl groups. The properties of these polymers with free radical groups are discussed in relation to their spectral data.
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    Enantioselektive Trifluoracetylierung mit Hilfe chiraler PolyamideHerrn Prof. Dr. Seefelder mit freundlichen Grüßen zum 60. Geburtstag gewidmet (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 643-649 
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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: (S)-Poly(2-aminobutyric acid) (1) [(S)-poly(imino-1-methyl-3-oxotrimethylene)] was transformed into its N-trifluoroacetyl derivative 4. The IR spectra and the circular dichroism of both substances were compared. In addition, (S)-poly[N-(1-phenylethyl)acrylamide] (2) ((S)-poly-[1-(1-phenylethylaminocarbonyl)ethylene]) was trifluoroacetylated leading to polymer 5. 4 was found to react as trifluoroacetylating agent with L-1-phenylethylamine (L-3) twice as fast as it reacts with D-3. Accordingly, the reaction of 4 with D,L-3 leads preferentially to the L-form of N-(1-phenylethyl)trifluoroacetamide with optical yields up to 6%. The reaction of 5 with D,L-3 affords the D-form of N-(1-phenylethyl)trifluorcacetamide with optical yields up to 13%.
    Additional Material: 3 Ill.
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    Terpolymérisation acrylonitrile  -  styrène  -  acrylate de méthyle, 1. Etude cinétique de la terpolymérisation en émulsion, en réacteur fermé (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 677-700 
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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: Binary and ternary copolymerizations of the acrylonitrile (A) / styrene (S) / methyl acrylate (M) system were carried out by emulsion polymerization, using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator. Kinetic studies of the reaction mixture by gas chromatography and simulation calculation of the copolymer composition versus conversion show that the classical theory of copolymerization (propagation rate by Markov chain 1st order) can be applied to the emulsion polymerization of this system, even at high conversion level. It was found that, when a conversion limit is obtained, the polymerization can be started again owing to a new addition of the more rapidly consumed monomer (styrene, in this case); it appears that both polymerization process and conversion effect do not involve appreciable variations of the polymer radical reactivity.
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    Studies of optical activity of poly(l-menthyl vinyl ether) (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 707-713 
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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 optical activities of poly(l-menthyl vinyl ether) (PMVE), obtained by cationic polymerization were studied. The polymerizations were carried out at various temperatures (-72 to +30°C), with different solvents and catalysts. The optical rotation of PMVE, which was polymerized with BF3O(C2H5)2 in toluene at -72°C, was found to be independent of the initial monomer concentration; but it depends on the activity of the catalyst. The absolute values of optical rotation of PMVE decreased with increasing temperature and dielectric constant of the solvent. The relationship between the optical activities of PMVE and the polymerization conditions is discussed.
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    Optically active vinyl polymers, 22.Part 21: cf. P. Pino, A. Allio, Helv. Chim. Acta 57, 616 (1974). Relationship between intrinsic viscosity and molecular weight for poly-(S)-4-methyl-1-hexene and related polymersDedicated to Professor H. Batzer on the occasion of his 60th birthday (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 737-749 
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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: Isotactic poly-(S)-4-methyl-1-hexene (PS4MH), poly-(R,S)-4-methyl-1-hexene (PRS4MH) and poly-4-methyl-1-pentene (P4MP) were fractionated according to stereoregularity and molecular weight. The fractions obtained were characterized and the constants aη and K of the Mark-Houwink equation calculated for thermodynamically good solvents at low temperatures and for theta solvents at high temperatures.
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    Living anionic stereospecific polymerization of 2-vinylpyridine, 1. Initiation of polymerization and stereoregularity of polymers (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 799-808 
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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: Initiation of the polymerization of 2-vinylpyridine by organomagnesium compounds in hydrocarbon solvents, was obtained without side reactions on the pyridine rings. The resulting active centres are unsymmetrical. They are stable and stereospecific, leading to living polymers with an isotacticity degree of about 0,9.
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    Propriétés viscoélastiques de la poly(α,α-diéthyl-β-propiolactone) (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 857-867 
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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 viscoelastic properties of poly(α,α-diethyl-β-propiolactone) were investigated in the linear range using stress relaxation and dynamic mechanical methods. Using Ferry's reduction method, a horizontal shift factor was determined at each temperature, that satisfactorily agreed with the WLF equation in the transition zone. No vertical shift was required to superimpose different relaxation curves. The apparent activation energy was temperature dependent and passed through a maximum near Tg whose value is (311 ± 2)K. The relaxation spectrum has been calculated according to the first method of approximation of Schwarzl and Staverman. It consists of a high intensity plateau at shorter times, a wedge type portion with a slope of -0,15 and a low intensity plateau at longer times. Dynamical mechanical measurements revealed a β relaxation peak at 333 K and yielded the evidence of a γ peak around 120 K.
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    Die thermische polymerisation von methylmethacrylat, 32. Mitteilung: cf.2.. Verhalten des ungesättigten dimeren bei der polymerisation (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 913-921 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The thermal polymerization of methyl methacrylate is accompanied by the formation of appreciable amounts of an unsaturated dimer (H-1). The behaviour of H-1 during homopolymerization in presence of an initiator at 60, 80 and 100°C and during copolymerization with MMA in presence of an initiator at 60°C are investigated. The rate of (H-1)-homopolymerization is very low. The transfer constant to monomer H-1 is about CH-1 = 3·10-3 at 80°C as received from Pn-determinations. The termination is essentially by disproportionation. The copolymerization parameters as resulting from polymerizations with labeled MMA at 60°C are rMMA = 1,8 and rH-1 = 0,33, respectively.
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    Study of surface potential characteristics of corona charged ethyl cellulose layers for its relevance in electrothermography (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 951-956 
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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 solution cast layer of ethyl cellulose on aluminium substrate shows high charge acceptance on corona charging. Its surface potential decay characteristics are studied at room temperature and at higher temperatures. Addition of a thermosensitive dye in the polymer matrix shows enhanced contrast potential at constant IR exposure. Optimum conditions for suitability of the polymer in electrothermography is determined by studies on different weight proportions of dye. The effect of layer thickness on surface potential characteristics is also investigated.
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    Haupt- und seitenkettenkristallinität bei isotaktischen poly(1-alkylethylen)en, 32. Mitteilung: cf.2.. Änderung der ordnungszustände bei den höheren homologen (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 969-977 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The higher homologues for isotactic (it) poly(1-alkylethylene)s (from it-poly(1-dodecylethylene) to it-poly(1-eicosylethylene)) show three polymorphic modifications. The modification of highest order crystallizes in an orthorhombic structure (modification I). This modification is formed during melt crystallization at a cooling rate φ 〈 2,5 K·s-1. The main-chain conformation is a quaternary helix. The side-chains are tilted 130,6° against the axes of the helices and crystallize like orthorhombic polyethylene. The DSC-curves of these homologues in modification I show the endotherm of melting and an endotherm at a temperature, about 25 K to 30 K below the melting temperature. The endotherm at the lower temperature is caused by atactic material in the samples, by only partially ordered crystallites in isotactic material, and by the change of conformation of some CH2-groups of the side-chains near the main chain.
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    Synthesis of a polydithiocarbonate from carbon disulfide, alkali metal diolate and α,ω-dihalo compound (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 979-984 
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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: Poly[thio(thiocarbonyl)oxy-1,4-cyclohexyleneoxy(thiocarbonyl)thiomethylene-1,4-phenylenemethylene] (4) was obtained from 4-bromomethylbenzyl bromide (1), dipotassium 1,4-cyclohexanediolate (2) and carbon disulfide at low temperature by using 1,4,7,10,13,16-hexaoxacyclooctadecane as catalyst. At high temperatures, poly[oxy-1,4- cyclohexyleneoxymethylene-1,4-phenylenemethylene] (8) was obtained from the reaction between 1 and 2, however. Mechanisms are proposed for these reactions.
    Additional Material: 2 Ill.
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    Functional metal-porphyrazine derivatives and their polymers, 5Part 4: cf.13.. Peroxidatic oxidation of guaiacol by Fe(III)-3,4,3′,4′,3″,4″,3‴,4‴-octacarboxyphthalocyanine (Fe(III)-oaPc) and Fe(III)-oaPc/polyelectrolyte systems (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1003-1012 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The oxidation of guaiacol by the Fe(III)-oaPc/H2O2 system is studied by using a stopped flow spectrophotometer. The maximum rate of oxidation reaction by this system amounts to about 1000 times that in the absence of H2O2. The kinetic investigation indicates that the reaction can be regarded as “an ordered two-substrates reaction” and that the oxidation reaction proceeds according to the peroxidase-like mechanism. The reaction is inhibited by adding cyanide. The structure of oxidation products is also discussed. The catalytic action of Fe(III)-oaPc in the presence of various polyelectrolytes such as poly(vinylamine) is also investigated, varying the pH values, and the environmental effect of the polymers in their catalytic behavior is discussed.
    Additional Material: 12 Ill.
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  • 140
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    NMR investigation on oligo- and poly(galacturonic acid)s; gel formation in the presence of Ca2+ counterions (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1059-1070 
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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: In this paper, the assignment of the 1H and 13C NMR spectra of poly(galacturonic acid)s is proposed; the 4C1 chair conformation of the monomeric unit in poly(galacturonic acid) is confirmed and the composition of the anomeric mixture at the reducing end (α-D)/(β-D) = 35 : 65 mol/mol independent of the degree of polymerization DP (2 ≤ DP ≤ 5) is given. It is demonstrated on oligomers that both 13C and 1H chemical shifts and coupling constants are nearly unaffected by exchanging Na counterions with Ca; the osmotic coefficient of Ca depends on the DP just as predicted by an electrostatic mechanism. The intrinsic viscosity of the polymer increases and the intensity of 13C NMR signals decreases suddenly for 0,3 equivalents Ca2+ per carboxylic site. These results confirm a multichain association followed by a rigid gel formation; the crosslink is proposed to correspond to a cooperative “egg-box” mechanism on chain segments randomly distributed in the gel.
    Additional Material: 4 Ill.
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  • 141
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    Solvent effect on the asymmetric induction copolymerization of styrene with maleic anhydride in the presence of lecithin (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1081-1088 
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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 asymmetric induction radical copolymerization of styrene (St) with maleic anhydride (MAn) was studied in various solvents with different dielectric constants in the presence of lecithin as a chiral surfactant. The observed specific rotation of the resulting alternating copolymer decreased with an increase in the dielectric constant of the solvent used. It was concluded that the asymmetric induction depends mainly upon the incorporation of MAn within the reversed lecithin micelles.
    Additional Material: 3 Ill.
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  • 142
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    The influence of spherulitic size on the environmental stress cracking of low density polyethylene (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1121-1126 
    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 morphology in a low density, high melt index polyethylene was studied with particular reference to environmental stress cracking (ESC). Test samples of the polyethylene were molded under constant conditions, only the subsequent rate of cooling to room temperature being changed. Several techniques were used to study the resultant polymer including ESC tests, X-ray diffraction, optical microscopy and constant strain rate stress/strain tests. It was found that the faster the polymer was cooled after molding, the smaller was the typical diameter of the spherulites and the greater the resistance to stress cracking. A hypothesis is proposed to explain the differences in terms of the ease with which a crack can propagate, assuming that propagation is easier in amorphous material than within spherulites.
    Additional Material: 3 Ill.
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  • 143
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    Hypochromism of polyhalogenvinylcarbazoles (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1209-1213 
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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: Spectrophotometric studies in the UV region were carried out for a series of chlorine and bromine derivatives of N-ethylcarbazole and poly(N-vinylcarbazole). All the examined polymers, in the whole spectral range, exhibit considerably less absorptivity than their low molecular models, i.e. ethylcarbazoles. Absorption bands of the polymers are shifted, in comparison to the respective absorption bands of halogenethylcarbazoles, towards shorter wavelenghts. Halogen substituents in the carbazole ring reduce the transfer energy π → π*. This bathochromic effect is especially observable for low-energy bands 1La and 1Lb, and it was noticed that the bromine substituent exerts more influence than the chlorine substituent.
    Additional Material: 3 Tab.
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  • 144
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    Struktureller aufbau und physikalisches verhalten vernetzter epoxidharzeHerrn Prof. Dr. H. Batzer zum 60. Geburtstag gewidmet (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1251-1287 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Network structures and physical properties of products obtained either by crosslinking polyepoxides with polyphenols, and by dicyanodiamide or by catalytic polymerization are discussed and compared with those obtained by amine or anhydride curing. The highest crosslinking density is achieved by the polymerization of epoxy compounds. In polymerization, the glass transition temperature may rise by more than Δ Tgv = 100 K. Amine and phenol curing result in similarly structured networks with mobile aliphatic segments and comparatively low crosslinking densities. Impact resistance based on dissipation of mechanical energy increases as network density decreases, a maximum being achieved with a medium chain length of 25 - 35 atom intervals between crosslinking points. The mechanical stability of polymers is limited by the cohesive strength KF. This latter corresponds to the maximum shear strength of bonds TKFmax, which was measured within the temperature range of 77 K to 450 K, in accordance with the equation \documentclass{article}\pagestyle{empty}\begin{document}$ {{\rm TKF}_{\max } = {\rm KF} = B - C \cdot T;} \quad {T 〈 T_g } $\end{document} This equation was derived from Eyring's model of viscosity, correlating B and C with activation volume, activation energy, Tg, and strain rate. B equals the cohesive strength at 0 K. It is determined by intermolecular forces but does not depend on the density of crosslinking. An increase of Tg due to crosslinks or bulky segments causes a decrease of C and therefore a reduction of the temperature dependence of KF. Hence, cohesive strength at room temperature is improved.
    Additional Material: 15 Ill.
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  • 145
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    Melting and crystallization behaviour of random copolymers from adipic acid, trans-3-hexenedioic acid and 1,16-hexadecanediol (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1339-1348 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Copolyesters derived from adipic acid, trans-3-hexenedioic acid and 1,16-hexadecanediol were prepared and investigated by means of X-ray diffraction and DSC techniques. From the X-ray results an isomorphous replacement of the saturated and unsaturated diacid units has been suggested. The equilibrium melting temperature Tm0 and the heat of fusion ΔHf were slightly dependent on the copolyester composition. The crystallization process was analyzed by means of Hoffman's kinetic crystallization theory for a lamellar type crystal growth. The values of the free energy of formation of a nucleus of critical dimensions φ* and the free energy of folding σe were found to decrease regularly with increasing amount of double bonds, varying from 110 to 83 kJ/mol for Δφ* and from 171 to 127 erg/cm2 for σe. This effect has been interpreted on the basis of an increase of chain flexibility owing to the presence of the trans double bonds.
    Additional Material: 7 Ill.
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  • 146
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    Melting temperatures and enthalpies of polyethers, 2Part 1: cf.7.. Poly(octamethylene oxide) (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1357-1362 
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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 dependence of the melting temperature on the crystallization temperature for low molecular weight fractions of poly(octamethylene oxide), (poly(oxyoctamethylene)), in the range from Mn = 3400 to Mn = 9 000, is analyzed. It is found that in this molecular weight region, the extrapolated linear relation melting temperature Tm vs. crystallization temperature Tc, for high levels of crystallinity yields an equilibrium temperature, which is in good accord with theoretical expectations; meanwhile the Tm vs. Tc relation for low levels of crystallinity leads to higher equilibrium temperatures. The equilibrium melting temperature corresponds to 356 K for Mn = 9 000 and the enthalpy of fusion was found to be 60,5 cal/g (= 253 J/g).
    Additional Material: 4 Ill.
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    Oligomérisation anionique de l'éthylène, 5Partie 4: cf.1. Fonctionalisation des oligomères vivants par action directe de l'oxygène (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1425-1434 
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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: Living oligomers of ethylene obtained by sec-butyllithium complexed with tetramethylethylenediamine (TMEDA) were deactived by oxygen. NMR and mass spectrometry, coupled with gas chromatography of the resulting product allowed us to follow the influence of TMEDA towards functionalization. The two products were characterized. Apparently the ratio [TMEDA]/[sec-BuLi] does not seem to influence the functionalization reaction.
    Additional Material: 3 Ill.
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  • 148
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    Polymere charge-transfer-komplexe auf der basis von polyvinylalkoholacetalen, 2I. Mitteilung: cf.25. (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1483-1494 
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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: Poly[2-(1-naphthyl)-1,3-dioxan-4,6-diylmethylene] (3), poly[2-(2-naphthyl)-1,3-dioxan-4,6-diylmethylene] (5), 1-naphthalenecarbaldehydetrimethyleneacetal (7) and 2-naphthalenecarbaldehydetrimethyleneacetal (8) were synthesized and characterized by UV- and fluorescencespectroscopy. In addition triplet-triplet absorption maxima and triplet-lifetimes were determined by flash technique. The naphthalene derivates were found to act as donors in the charge-transfer complex formation with such electron acceptors as tetracyanoethylene, 2,5-cyclohexadien-1,4-diylidenedimalonodinitrile and 2,4,5,7-tetranitro-9-fluorenone. The equilibrium constants of the charge-transfer complexes were determined spectrophotometrically by the methods of Benesi-Hildebrand, Benesi-Hildebrand-Scott and Foster-Hammick-Wardley.
    Additional Material: 6 Ill.
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    Darstellung und [η]-M̄-Beziehung von Mikrogelen aus polyvinylalkoholProf. Hans Wilhelm zum 60. Geburtstag gewidmet (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1513-1524 
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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: Microgels were prepared by crosslinking of poly(vinylalcohol)s with different molecular weights (saponification degree: 88 mole-%) with glutaraldehyde in aqueous solutions. The degree of crosslinking was varied between 0 and 10% (i.e. 10 crosslinks per 100 structural units). Viscosity measurements showed that the viscosity number [η] of the microgels decreases considerably with increasing degree of crosslinking  -  as to be expected with increasing mean density of the random coils: The mean coil volume in aqueous solution shrinks by introducing 10 crosslinks per 100 structural units to 1/10 of the primary volume. A comparison of the logarithmic [η]-M̄-plots of our microgels showed a linear decrease of the exponent a, from a = 0,73 (uncrosslinked) to a = 0,16, with increasing degree of crosslinking. By extrapolation, with a degree of crosslinking of 13% (i.e. 13 cross-links per 100 structural units of polymer chain), it was found that [η] becomes independent of the molecular weight of the primary PVAl-samples.
    Additional Material: 9 Ill.
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  • 150
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    Copolymerisation von 4-(1,1-dicyanoethylazo)benzylmethacrylat mit styrol, methacrylonitril und methylmethacrylat mit anschließender Pfropfung der Azocopolymere (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1565-1577 
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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: 4-(1,1-Dicyanoethylazo)benzyl methacrylate (3), a new azo-monomer, was copolymerized with styrene, methacrylonitrile, and methyl methacrylate (MMA) giving azo-copolymers. The compositions of the copolymers from 3 and MMA were nearly identical with those of the monomer mixtures. Thus allowing 100% conversion leading to copolymers of almost identical chemical composition. These azo-copolymers were used as initiators for different monomers in either emulsion or solution, resulting in graft-copolymers. The graft-copolymers were characterized by IR and GPC. In one case the raw graft-copolymer was separated into ungrafted backbone-polymer, grafted copolymer, and homopolymer of the component to be grafted.
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  • 151
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    Copolymerization of carbon dioxide with propylene oxide catalyzed by O-methylated or crosslinked poly(p-hydroxystyrene)/diethylzinc system (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1613-1618 
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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: Effective catalysts for the copolymerization of CO2 with 1,2-epoxypropane were prepared from partially O-methylated or crosslinked poly[1-(4-hydroxyphenyl)ethylene] and Zn(C2H5)2. The highest activity was obtained with catalysts of 30 to 40% methylation or crosslinking. Inactivation of the catalysts during the copolymerization was decreased by crosslinking, increasing the yield of the copolymer. The higher rigidity of the catalyst structure is responsible for its higher activity and stability.
    Additional Material: 4 Ill.
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  • 152
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    Solution properties of poly(N-1,1-dimethyl-3-oxobutylacrylamide), 2Part 1: cf.1. Excluded volume in 2-butanone at 25°C (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1649-1654 
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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 excluded volume parameter B for poly(N-1,1-dimethyl-3-oxobutylacrylamide) in 2-butanone at 25°C is evaluated either from limiting viscosity numbers or from second virial coefficients as obtained in light scattering measurements, and also through a procedure in which both kinds of experimental data are simultaneously employed. The values so obtained are in reasonable agreement, except for the one evaluated by applying the original Stockmayer-Fixman equation, which is largely underestimated as already found for other polymer-solvent systems.
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    Elektron-Donor-Akzeptor-Komplexe und copolymere mit difluormaleinsäureanhydridAuszugsweise vorgetragen auf dem Makromolekularen Kolloquium, Freiburg, März 19781. (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1703-1715 
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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 formation constants of electron donor acceptor complexes formed by p-dioxene, α-methylstyrene, phenanthrene, phenyl vinyl ether and styrene as donor molecules and difluoromaleic anhydride as acceptor are much larger compared to those formed by maleic anhydride and the same donor molecules. However, no relation can be established between the numerical value of the formation constant and the tendency of alternating copolymerization induced by radical initiators. Symmetry considerations lead to the conclusion that electron donor acceptor complexes have no significant involvement in this copolymerization. The result of our kinetic investigations in the system phenyl vinyl ether/difluoromaleic anhydride supports the above statement: The formation of the electron donor acceptor complex is not the rate determining step of copolymerization.
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  • 154
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    Influence of composition on the melt crystallization of isotactic random propylene/1-butene copolymers (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1747-1755 
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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 influence of composition on the overall rate of isothermal crystallization of isotactic random propylene/1-butene copolymers is investigated. At a constant crystallization temperature a small fraction of 1-butene co-units inserted along a polypropylene chain causes a drastic reduction in the overall rate of crystallization. Further it is found that for a given rate of crystallization it is possible to crystallize the isotactic polypropylene at lower crystallization temperature by adding along the chain a small amount of 1-butene as comonomer. The equilibrium melting temperature, the surface free energy of folding, the enthalpy and the entropy of fusion decrease with increasing the contents of 1-butene in the copolymer samples.
    Additional Material: 9 Ill.
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    Kinetik und mechanismus der kationischen polymerisation von trioxan: Ein katalysierter kristallwachstumsprozeßHerrn Prof. Dr. Dr. h. c. H. Pommer anläßlich seines 60. Geburtstages gewidmet (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1763-1790 
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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 kinetics of the cationic polymerization of trioxane initiated by perchloric acid is analyzed as a simultaneous polymerization and crystallization process. The details of the crystal growth such as nucleation, distribution of crystal sizes, development of growth spirals etc. have been investigated by electron and light microscopic techniques. The mechanism of polymerization can be understood as a catalyzed crystal growth. A well defined population of crystals is formed during a nucleation event at the start of the polymerization. An adsorption equilibrium with regard to the catalyst is then established in the presence of the rather large surface area of the growing polymer crystals. Assuming a Langmuir-type adsorption behaviour, the observed growth features (growth spirals) can be quantitatively interpreted on the basis of the BCF-theory of crystal growth. The current concepts on the molecular mechanism of cationic polymerization of cyclic formals have been modified such as to take into account that each chemical step of the polymerization is a building step of the crystal too.
    Additional Material: 24 Ill.
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    Study on the complex formation of cobalt chelates with polymer ligands (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1823-1840 
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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: Variously composed copolymers from styrene and 4-vinylpyridine (4-VP) were prepared and their complex formation reactions with benzylbis(dimethylglyoximato)Co(III) [BzCo(III)(DMG)2] and N,N′-ethylenebis(salicylideneiminato)Co(II) (Co(II)salen) were studied kinetically by the stopped-flow rapid scanning spectroscopy. For the complex formation reaction with BzCo(III)(DMG)2, the relationship between the complex formation constant K and the content of 4-pyridylethylene units in the copolymers showed an unusual bell-type curve, and the K values were higher than the K value of complexation with pyridine. From the correlation between K, k (complex formation rate constant), and k′ (complex dissociation rate constant), it resulted that (1) the higher K values of the polymer systems are due to the lower k′ values compared with the pyridine system, and (2) the bell-type change of the K values is also caused by the k′ values. In the case of Co(II)salen-copolymer systems, two species of the complex, i.e., mono- and diaxial coordinated complexes were clearly identified by spectrometric kinetics, whereas the pyridine system gave only a mono-axial coordinated complex. The diaxial coordination seems to lead to a much more favorable structure than the monoaxial one, due to the entropic gain or to the polymer chelate effect.
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    Esterolytic action of poly[p-vinyl(thiophenol)-co-acrylic acid] (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1889-1896 
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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: Hydrolyses of p-nitrophenyl acetate (PNPA) and 3-acetoxy-N,N,N-trimethylanilinium iodide (ANTI) catalyzed by poly[p-vinyl(thiophenol)-co-acrylic acid] (PSH) were studied in the pH range of 8 - 9,5. The reaction of PNPA followed pseudo-first-order kinetics and was found to be catalyzed by the thiophenolate ions on the polymer backbone. In the case of positively charged ANTI, the rate of catalysis showed substrate saturation phenomena and could be described by a Michaelis-Menten kinetics. This indicates that this reaction proceeds via a complex formed by electrostatic interaction between the substrate and the negatively charged polymer catalyst. When ionic strength was increased to 0,12 mol/l the reaction did not further follow the Michaelis-Menten kinetics, suggesting that the complexation constant or the reaction rate of the complex might vary with the amount of the substrate incorporated in the polymer domain. Positively charged N,N,N-trimethylanilinium iodide competively inhibited the PSH-catalyzed hydrolysis of ANTI.
    Additional Material: 7 Ill.
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    Nuclear magnetic resonance studies on polymer carbanions, 1. Living polystyrene and its model compounds (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1923-1934 
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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: 1H and 13C NMR investigations were carried out on polystyryl carbanions and model compounds for the active chain end of living polystyrene, changing counter cation (Li, K, and Cs), solvent, and temperature. The structure of the model compounds with K and Cs as counter cation was planar with sp2-hybridized α-carbon, which indicates strongly hindered rotation of the phenyl ring. For the model compound with lithium as counter cation, the phenyl ring rotation was hindered at lower temperatures. The 13C—1H coupling constants of the compound indicated less sp2 character of α-carbon. The differences in the chemical shifts of the two ortho or meta carbons depended on the type of counter cation, suggesting an interaction between counter cation and phenyl ring. Quantum chemical calculations on the structure of the model compounds were carried out and the results were compared with the excess charge distributions calculated from 13C NMR chemical shifts.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1980.021810913
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  • 159
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    X-ray and neutron small-angle scattering of random coil polymer solutions (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1987-1998 
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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: Small-angle scattering curves of random coil polymer solutions are calculated from the general scattering theory of solutions by making use of a previous calculation of the Yvon-Born-Green integral equation for the radial distribution function of the solute polymer molecules. The calculated scattering function is a monotonously decreasing function of the scattering angle at low polymer concentration, and it has a minimum and a maximum at high concentration, where the polymer interaction is repulsive. For large scattering angle, the reciprocal values of the scattering function increase almost linearly with sin2(θ/2), where θ is the scattering angle. This calculated result is in qualitative agreement with recent experimental results of X-ray and neutron small-angle scatterings of polymer solutions.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1980.021810918
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  • 160
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    Darstellung von neuen makromolekularen stoffen aus derivaten der 3-aminocrotonsäure und dimaleinimidenHerrn Prof. Dr. H. Batzer zum 60. Geburtstag gewidmet (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 2025-2047 
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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: Cross-linked polymers are formed by a new addition polymerization of dimaleinimides with bis(3-aminocrotonic acid)-esters, -amides, or -nitriles. Model reactions show that the derivatives of 3-aminocrotonic acid add to the electrophilic double bond of maleinimide. The resulting succinimid derivatives rearrange thermally to the corresponding pyrrolinones. At higher temperatures, especially in the presence of an excess of maleinimide, a second molecule of maleinimide is added to the pyrrolinone. Some properties of moulded and casted polymers are described.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1980.021811002
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    Reactions of polyamide 6 and 6,6 with 1,5-difluoro-2,4-dinitrobenzene: Photometric technique for the determination of the degree of crosslinkingPresented at “Makromolekulares Kolloquium”, Freiburg, W.-Germany, 1.3.79.Dedicated to Professor Dr. rer. nat. Matthias Seefelder on the occasion of his 60th birthday (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 2071-2079 
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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: During the reaction of polyamide 6 or polyamide 6,6 with the bifunctional crosslinking agent 1,5-difluoro-2,4-dinitrobenzene in heterogeneous media, 5-fluoro-2,4-dinitrophenylamino groups and 4,6-dinitro-1,3-phenylenediamino groups are formed within the polymer. Owing to their different VIS-spectroscopic behaviour, the concentration of both groups can be determined by means of a bicomponent analysis, \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {c_1} & {= (15,36 \cdot A_{375} - 6,35 \cdot A_{425}) \cdot 10^{- 5} ({\rm mol} \cdot {\rm dm}^{- 3})} \\ {c_2} & {= (9,48 \cdot A_{425} - 4,78 \cdot A_{375}) \cdot 10^{- 5} ({\rm mol} \cdot {\rm dm}^{- 3})}\\ \end{array}$$\end{document} where c1 and c2 represent the concentration of 5-fluoro-2,4-dinitrophenylamino and 4,6-dinitro-1,3-phenylenediamino groups, respectively, and A375 as well as A425 represent the absorbances at 375 nm and 425 nm, measured in a 1 cm cell (solvent: 2,2,2-trifluoroethanol). N-(5-fluoro-2,4-dinitrophenyl)-ε-aminocaproic acid and N,N'-(4,6-dinitro-1,3-phenylene)-di-ε-aminocaproic acid are used as model compounds in order to calibrate the photometer. It is demonstrated that the degree of crosslinking, determined by means of the bicomponent analysis, is in accordance with the change of molecular weight, determined viscosimetrically.
    Additional Material: 3 Ill.
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  • 162
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    Polymere phthalocyanine und ihre vorstufen, 1. Reaktive oktafunktionelle phthalocyanine aus 1,2,4,5-tetracyanbenzol (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 2127-2135 
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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: 1,2,4,5-Tetracyanobenzene reacts under mild conditions with anionic reagents not to polymer but to low molecular weight, high substituted phthalocyanines: 2,3,9,10,16,17,23,24-octacyanophthalocyanine (3a) and tetrakis(1-imino-3-propoxyisoindolo)porphyrazine (3b). 3a is saponified to the octacarboxyphthalocyanine 3c and converted with hydrazine to tetrakis(1,4-diaminophthalazino)porphyrazine (3d). Low molecular metal chelates are synthesized starting from 3a and 3c. IR- and UV/VIS-spectra are discussed.
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  • 163
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    Thermodynamic studies on DNA-dye complexes (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 2175-2181 
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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 interaction between DNA and dyes such as acridine orange (1), proflavine (2), and 3,8-diamino-5-ethyl-6-phenylphenanthridinium bromide (3) were studied by means of the heat of mixing and UV spectra. From the results obtained, the thermodynamic quantities of DNA-dye complexes were estimated. It is concluded that the intercalation process forms a more stable binding than the stacking process does. Further, in each process, ΔG of DNA-2 and DNA-3 systems is nearly equal to that of the DNA-1 system, but their  -  ΔH and  -  ΔS values are higher than those of the DNA-1 system. The stability of binding in DNA-2 and DNA-3 systems may be governed largely by ΔH, while in the DNA-1 system ΔS may contribute largely to the stability of binding.
    Additional Material: 4 Ill.
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  • 164
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    Donor acceptor interactions in polymeric systems, 6.Part 5: cf.5. Effects of the molecular weight of carbazolyl containing polyesters and the length of spacer between donor groups on the complex formation with 2,4,7-trinitrofluorenone (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 2207-2215 
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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: EDA complex formation between 2,4,7-trinitrofluorenone (TNF) and polyesters bearing pendant 9-carbazolyl groups was studied in ethylene dichloride. The formation constant (K) decreases with increasing length of the main chain repeating units separating pendant donor groups and with decreasing degree of polycondensation. In all cases, the values of K in polymeric systems are larger than those for the monomer model system by factors less than three. Thermodynamic parameters for complex formation were also determined. The general trend of the polymer effect is to increase - ΔH, while the entropy term is not much different from the monomer model system. The origin of polymer effects is interpreted as due not only to neighbouring group effects but also to remote group effects, and simultaneous participation of more than one carbazolyl group in complexing an acceptor molecule is considered. The results are compared with the EDA complex formation by ethylenic polymers and polyurethanes with pendant carbazolyl groups.
    Additional Material: 4 Ill.
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  • 165
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    Synthesis of new monomers having a primary amino group by lithium alkylamide catalyzed addition reaction of N-alkylethylenediamines with 1,4-divinylbenzene (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 2251-2257 
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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: Lithium alkylamide catalyzed addition reaction of N-alkylethylenediamines (1) with styrene was examined. It was found that N-alkyl-N-(2-phenethyl)ethylenediamine (3) was formed selectively in preference to N-alkyl-N′-(2-phenethyl)ethylenediamine (4). The identification of products was carried out by 13C NMR. On the basis of the results obtained, a new type of styrene derivative having a primary amino group (6) was synthesized by lithium alkylamide catalyzed addition reaction of 1 with 1,4-divinylbenzene.
    Additional Material: 4 Ill.
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  • 166
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    Isotactic poly(allyl vinyl ether), 2. An NMR-study of stereoregularity and relaxation times (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 2385-2393 
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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 stereoregularity of poly(allyl vinyl ether), (poly[1-(allyloxy)ethylene], 1) was studied by both 1H- and 13C NMR-spectroscopy at 6,34 tesla. Even at this field the 1H NMR-resonances severely overlap, thus hampering a reliable analysis. The situation is far better for the 13C NMR-resonances; here even hexad splittings could be observed. Relaxation time ratios of the backbone carbon atoms are consistent with a dipolar relaxation mechanism. The relaxation time for the racemic peak is longer than that for the meso peaks, which is in contrast with literature data for other polymers7,8. This deviating behaviour could be accounted for by the higher magnetic field used in our measurements.
    Additional Material: 7 Ill.
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    Structure and properties of segmented poly(ether esters), 4Part 3: cf.5.. Compatibility of oligo(tetramethylene terephthalate)s with oligoethers and block copoly(ether ester)sHerrn Prof. Dr. G. V. Schulz zum 75. Geburtstag gewidmet (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 2357-2363 
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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 mutual compatibility of oligo(tetramethylene terephthalate)s 1a - d and their compatibility with oligoethers 2, 3, and 4 and block copoly(ether ester)s 5a - c based on poly(tetramethylene terephthalate) and poly(oxytetramethylene) is reported. From the binary phase diagrams of the oligoesters it is concluded that the oligoesters do not cocrystallize and the melt of the lower melting compound is not a good solvent for the higher melting homologue. For the trimer/pentamer (1b/1c)-blend the eutectic composition contains 3 mole-% of the pentamer 1c. Oligo(oxytetramethylene) (3) is a better solvent for the oligoesters than oligo(oxyethylene) (2). The addition of an oligoester to the block copoly(ether ester) induces a change in the phase behaviour of the polymer, resulting in a melting point of the blend higher than for the pure polymer or oligomer.
    Additional Material: 5 Ill.
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    On the molecular weight determination by vapour pressure osmometry, 1. Consideration of the calibration function (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 2401-2407 
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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 detailed study on the calibration of vapour pressure osmometry (VPO) using thirteen different samples (eight of them polystyrenes) in a range of molecular weights up to 50 000 as solutes and chloroform, dichloromethane, ethyl methyl ketone, cyclohexane, and acetone as solvents is carried out. The results show that contrary to the commonly used calibration equation M = K · (ΔV/c)c=01, the relationship between the measuring result (ΔV/C)c=0 and molecular weight M obeys a function of the type M = K · (ΔV/c)c=0a in which the exponent a differs from 1. For each of the above mentioned solvents the values of K and a are determined. The limits of applicability of VPO with respect to polymers are discussed in view of these terms and recent theoretical considerations.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1980.021811118
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  • 169
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    Coordination polymers of β-hydroxy-γ-amino schiff bases (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 2441-2448 
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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: Ligands 3a-d (N,N-disubstituted 2,2′-dihydroxy-3,3′-[1,4-phenylenebis(methylenenitrilo)]-dipropaneamines) for the preparation of the coordination polymers of Ag(I), Cu(II), Zn(II), and Ti(IV) were synthesized by condensation of terephthalaldehyde (2) with the N,N-substituted 2-hydroxy-1,3-propanediamines (1a-d). The copper and zinc coordination polymers were found to be compatible with polyethylene. Their blends could be processed by injection molding or extrusion. The thermal stability of the polymers was found to increase in the order Cu- 〈Ag- 〈Ti- 〈Zn-derivatives. The electronic, IR, and ESR spectra of the copper coordination compounds were measured and the mechanism of formation of the coordination polymers is discussed. The polymers were found to be semi-conductive, their electric resistivity being in the range of 103 - Ω·cm. The temperature dependence of the conductivity yielded activation energies in the range of 26 -106 kJ·mol-1. Both electronic and ionic conductance may contribute to the semiconductive properties of these coordination polymers.
    Additional Material: 4 Ill.
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    Cationic degradation of poly(2,3-dimethylthiirane)s: A method for microstructure determination of the polymers (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 2481-2493 
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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: Poly(cis-2,3-dimethylthiirane) and poly(trans-2,3-dimethylthiirane)  -  poly(cis-DMT) and poly(trans-DMT)  -  obtained by different polymerization mechanisms are degraded to cyclic compounds containing at least two structural units by treatment with a catalytic amount of a strong alkylating agent such as triethyloxonium tetrafluoroborate or methyltrifluoromethyl sulfonate (“methyl triflate”). The main degradation product is 3,4,6,7-tetramethyl-1,2,5-trithiepane and an equimolar amount of 2-butene. The trithiepane can exist as six different geometrical isomers which can be separated by GL-chromatography. Poly(trans-DMT) leads to the two isomers where both pairs of vicinal methyl groups are in trans position to each other. The ratios fo the two isomers can be correlated with the microstructure of the starting polymers. This was proved by degradation studies of optically active poly(cis-DMT): the higher the optical activity the higher the ratio of two isomers in the degradation mixture. The results indicate that the polymers (also the optically active polymers) do not show Bernoullian statistics, the number of isotactic diads (or triads) always being higher than expected.
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    Studies with microgels as matrices for molecular receptor and catalytic sites: The exceptional reactivity of hydroxyaminocarbonyl groups in polymers with a high level of cross-linking monomer feed (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 2529-2540 
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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 copolymer was prepared under emulsion conditions from a feed composed of methyl methacrylate, ethylene dimethacrylate, and 4-nitrophenyl acrylate in the mole ratio 0,57:0,14:0,29, respectively. Treatment with hydroxylamine gave a modified polymer with carboxylic and hydroxyaminocarbonyl residues in the mole ratio 22:3,7. The polymer molecule had a diameter of 400 Å and an approximate molecular weight of 18 000 000. The polymer-catalysed cleavage of 4-nitrophenyl esters depends on the fraction of ionised hydroxyaminocarbonyl groups (FB), and at low values of FB the reactivity (kn = dk2/dFB) is some 30-fold less efficient than that of monomeric hydroxamic acid of similar pKa. The value of kn increases with FB; at values of FB close to unity, kn exceeds that at low values by an amount in excess of 30 000. The value of kn at full ionisation is some 1 000-fold larger than that of the monomeric species. The macromolecules are permeable to substrates despite the high percentage of cross-linking, and it is proposed that the exceptional enhancement is due to the hydrophobic microscopic medium for the reaction of the last groups to ionise together with the high negative charge. It is proposed that the hydroxyaminocarbonyl groups with high reactivity are acting at the core of the macromolecule, whereas those at low values of FB are surface moieties. A cage effect also operates, holding the substrate in the vicinity of the nucleophile. The macromolecules exhibit an exclusion effect particularly marked for negatively charged substrates, which do not show significant curvature in plots of rate constant versus FB. 4-Nitrophenyl caproate also does not exhibit a large activation with increase in FB, and this substrate may only be partially excluded from the macromolecular core.
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    Photopolymerization of methyl methacrylate using quinoline-chlorine charge transfer complex as the photoinitiator (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 2597-2603 
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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: Photopolymerization of MMA was carried out at 40°C in bulk and in diluted systems using quinoline-chlorine (Q-Cl2) C.T. complex as the photoinitiator. Bulk polymerization followed normal free radical kinetics (initiator exponent = 0,5) for [Q-Cl2] 〈0,0015 mol.1-1. In diluted systems, variable monomer exponents were observed, ranging from slightly above 1 to 2,7, depending on the nature of the solvent (benzene, carbon tetrachloride, chloroform, chlorobenzene, acetone, dioxane, THF and DMF). Initiator exponent was ≤0,5 in diluted systems and it even became practically equal to zero depending on the nature of solvent and the level of dilution. The kinetic non-ideality in diluted systems was explained on the basis of solvent-retardation and initiator-termination via degradative chain transfer involving solvent-modified initiating complexes and chain radicals. The actual initiating complex appeared to be the (Q-Cl2)-monomer complex formed instantaneously in situ on addition of Q-Cl2 complex to the monomer.
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    Study of the interaction between trans-trans-trans-1,5,9-cyclododecatriene and dinitrogen tetraoxide as a model reaction of polybutadiene rubber nitration (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 2587-2595 
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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 reaction of trans-trans-trans-1,5,9-cyclododecatriene (1) with dinitrogen tetraoxide in tetrahydrofuran solution was studied as a model reaction of polybutadiene nitration. The reaction products were characterized by means of chemical and physical methods and the reaction process is discussed from a kinetic point of view. Attempts were made to explain the reaction mechanism at the initial steps of the nitration. The similarity between the reaction products and the kinetic results with those observed in the reaction of polybutadiene rubber nitration shows 1 to be a convenient model.
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    Peroxo salts as initiators of vinyl polymerization, 5Part 4: Cf.: S. P. Manickam, K. Venkatarao, N. R. Subbaratnam, J. Polym. Sci., Polym. Chem. Ed., in press.. Kinetics of polymerization of N-vinyl-2-pyrrolidone by peroxodisulfate in aqueous solution. Effect of Ag+ and Cu2+ ions (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 2637-2642 
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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 kinetics of the polymerization of N-vinyl-2-pyrrolidone by peroxodisulfate ion in aqueous solution in the presence and absence of metal ions Ag+ and Cu2+ is studied. The rate laws for the polymerization are established and the kp/kt1/2 values computed. A negative salt effect is observed for the Ag+ catalysed process, indicating the formation of a complex of the type AgS2O8- (aq). Cu2+ ions, however, are found to reduce the rate of polymerization.
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    The synthesis of stereoregular polymers by vinyl, ring-opening, and condensation polymerization reactions (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 4 (1981), S. 47-59 
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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 important factors which control the stereochemistry of polymerization, and thereby the crystalline properties of the polymers so formed, are considered for four different types of reactions including: (1) the cationic polymerization of substituted α-methylstyrenes to form syndiotactic polymers; (2) the anionic ring-opening polymerization of substituted β-propiolactones to form crystalline polyesters; (3) the metathesis ring-opening polymerization of 1,5-cyclooctadiene to form poly(1,3-butadiene)s of controlled cis-trans contents; and (4) the condensation polymerization of α-methylbenzyl chloride to form isotactic poly(α-methylbenzyl).
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    Sequence regulation in spontaneous binary and ternary copolymerizations via zwitterion intermediates (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 4 (1981), S. 73-84 
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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: This paper is concerned with the sequence regulation of monomeric units in a series of binary and ternary copolymerizations which proceed without any added catalyst or initiator. The binary copolymerization is consisted of the combination of a nucleophilic monomer (MN) and an electrophilic monomer (ME). The interaction between the two monomers generates a zwitterion of a 1:1 adduct, which is the key intermediate in the copolymerization producing 1:1 alternating copolymer. The varieties of MN and ME monomers, the structures of key intermediates of zwitterions, and the schema of copolymerizations have been discussed. In addition, the “Sequence-Ordered 1:1:1 Terpolymerization” (producing terpolymers of a type .…ABCABCABC….) and “2:1 Binary Copolymerization” (producing copolymers of a type of .…ABBABBABB….) are described, which have been developed on the basis of the above binary 1:1 alternating copolymerization.
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  • 177
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    Mismatched bases in nucleic acids: their effects on structures and stability (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 4 (1981), S. 143-153 
    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 ribo- and deoxyribo-oligonucleotides were synthesized with the sequences CAnG, CUmG AND CTmG (n and m = 5 or 6). These molecules can form RNA, DNA and hybrid double stranded helices containing either perfect base pairing (n = m), or mismatches (n ≠ m). The thermodynamics of formation of these helices has been measured and the destabilization caused by an extra uridylic, thymidylic or adenylic residue has been determined. Nuclear magnetic resonance of exchangeable imino protons has been used to study the conformations of the different helices. The binding of ethidium to the helices has been studies.
    Additional Material: 6 Ill.
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  • 178
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    Morphology and viscoelastic properties of isotropic and oriented polypropylene films (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 4 (1981), S. 207-222 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The physical structure of semicrystalline polymers influences many of their properties. It has been shown that thermal treatment (rate of cooling and annealing) as well as the action of mechanical forces (drawing) of isotactic polypropylene (PP) resulted in materials with different mechanical properties. In the case of isotropic films the crystallization temperature or annealing temperature from the glass and consequently morphological structure which has been formed, determine the values of modulae, yield stress and viscoelastic properties. Reoptical behaviour has been found to be sensitive to structural differences too. The structure and mechanical properties of highly oriented PP samples which have been obtained by drawing through a flat die have been found to be dependent on parameters characterizing this process (drawing rate, apex angle of die and elongation ratio).
    Additional Material: 20 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.020041981115
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  • 179
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    Catalytic behaviour of metalcomplexes immobilized in functional polymeric carriers (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 5 (1981), S. 121-154 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The general principles of construction of gel-immobilized catalyst systems (GICS) are reported as well as some peculiarities of the polymerization of ethylene and of the dimerization of ethylene and propylene in the presence of these systems.GICS consist of a transition metal complex and a specially designed polymeric support. Advantages offered by gel-immobilized catalyst systems are discussed with respect to homogeneous and microheterogeneous metal complex catalysts.
    Additional Material: 14 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.020051981109
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  • 180
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    Polymerization of epoxides catalysed by metalloporphine (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1073-1079 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The catalyst system obtained by the equimolar reaction of diethylaluminium chloride with α,β,γ,δ-tetraphenylporphine exhibits high catalytic activity in the polymerization of propylene oxide to give a polymer with a narrow molecular weight distribution. Average molecular weight of the polymer can be controlled by the initial mole ratio of propylene oxide to catalyst or by the conversion. Ethylene oxide also produces a polymer having a narrow molecular weight distribution.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820408
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  • 181
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    The influence of molecular interaction on polymerization, 5.Part 4: H. Boudevska, C. Brutchkov, V. Veltchev, Eur. Polym. J. 15, 907 (1979). Copolymerization of benzyl methacrylate with maleic anhydride (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1119-1125 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Copolymerization of benzyl methacrylate (BMA) with maleic anhydride (MA), initiated by 2,2′-azoisobutyronitrile at 70°C in chloroform or acetonitrile, were investigated. The complex formation between the two monomers in chloroform was studied by 1H NMR spectroscopy. The stability constant of the complex was found to be 0,25 l.mol-1. The following copolymerization reactivity ratios were found: in chloroform: rBMA = 0,188 ± 0,035 and rMA = 0,003 ± 0,005, in acetonitrile: rBMA = 0,116 ± 0,093 and rMA = 0,231 ± 0,027. By 1H NMR investigations it could be shown that the results correlate with the changes of the reactivity ratios depending on the solvent used.
    Additional Material: 2 Ill.
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  • 182
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    1H and 13C NMR studies on N-acetyl-L-alanyl-L-alanine-methylamide (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1153-1165 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 1H and 13C NMR spectra of N-acetyl-L-alanyl-L-alaninemethylamide and N-acetyl-L-alanyl-L-alanine methyl ester were measured in [2H]6-dimethyl sulfoxide and deuteriochloroform/trifluoroacetic acid solutions. The assignments of the N-terminal and internal NH proton peaks of the amide could be made by means of deuterium exchange experiments in [2H]6-dimethyl sulfoxide solution. An association model of the amide with an antiparallel β-sheet structure was proposed by taking into account the presence of an IR absorption at 1 690 cm-1 as amide I band and the results of the measurement of 3JHN-CαH coupling constants, as well as the deuterium exchange experiment. Moreover, the interaction between the peptide units in these two compounds and trifluoroacetic acid seems to be weaker than the N-acetyl-L-alaninemethylamide-acid interaction in a deuteriochloroform/trifluoroacetic acid solvent system of the same concentration.
    Additional Material: 10 Ill.
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  • 183
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    Copolymères du chlorure de vinylidène avec l'acrylonitrile, le chlorure de vinyle et le méthacrylate de méthyle, 2.Partie 1: cf.4. Fusion  -  utilisation d'un modèle de simulation (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1207-1214 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melting point depression in vinylidene chloride copolymers, when introducing an increasing number of units B = vinyl chloride, acrylonitrile or methyl methacrylate is studied in this paper. A Monte-Carlo simulation model of chains growing and crystallization is applied and allows to know the proportion Xc of defects in the crystalline phase. An equation given by Sanchez is then applied, and the excess energy ε of the defect created by the incorporation of a B unit in the crystalline vinylidene chloride lattice is calculated.
    Additional Material: 3 Ill.
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  • 184
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    Time resolved small angle scattering during isothermal crystallization of unoriented poly(ethylene terephthalate) using synchrotron radiation (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1263-1269 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The time course of the small angle scattering pattern of amorphous poly(ethylene terephthalate), (PET), was measured during isothermal crystallization using synchrotron radiation. The samples were heated to temperatures between 117 and 145°C in an oven placed in the path of the X-ray beam. The scattering curves were measured within 10 s at intervals of 1 s so as to follow the kinetics of the process continuously. It appears that the distance between the centres of mass of the crystallites decreases with increasing crystallization time as in oriented PET. The integrated small angle scattering follows approximately the same time course as the increase in the degree of crystallinity during an isothermal crystallization yielding Avrami exponents between 5 and 7. Guinier plots of the low angle region show that the scattering can be attributed to rod-like particles.
    Additional Material: 6 Ill.
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  • 185
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    Substituted and branched polychalcones. Syntheses and characterization by spectrometric methods (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1307-1317 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polychalcones 4a, b were prepared by a Friedel-Crafts acetylation of vanillin (3a) and p-hydroxybenzaldehyde (3b) and by a Fries rearrangement of the acetates in nitrobenzene using AlCl3 as catalyst. The reaction was carried out in one step under a variety of reaction conditions (time and temperature). The polymers were characterized by UV, IR and 1H NMR spectroscopy. The polychalcones obtained from p-hydroxybenzaldehyde had a limited solubility, but they swoll in DMSO and in dilute NaOH.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820502
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  • 186
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    Thermal decomposition of flame retardant acrylonitrile polymers, 2Part 1: cf.1.. Effect of red phosphorus (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1301-1306 
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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: Elemental red phosphorus was found to be an efficient flame retardant for poly(acrylonitrile) homopolymer (PAN) and, to a lesser extent, also for a modified acrylic resin containing 36 wt.-% of vinylidene chloride (VC2) as comonomer. The data collected show that condensedphase and gas-phase mechanisms are both responsible for the flame inhibition effect of red phosphorus on PAN. On the contrary, a gas-phase mechanism seems to be responsible for the flame inhibition effect of red phosphorus on the AN-VC2 copolymer. Flash-pyrolysis GC data, with pyrolysis products MS identification, are reported for both polymers studied.
    Additional Material: 6 Ill.
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  • 187
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    Syntheses of diacetylene monomers from N-(nitrophenyl)amine substituted diacetylene alcohols (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1363-1370 
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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: Several new classes of asymmetric diacetylene monomers of the type O2N—Ar—NH—CH2—C=C—C=C—CH2—R have been synthesized from nitroaniline diacetylene alcohols. The solid state polymerization behavior of several members of these classes has been examined.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820507
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  • 188
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    Hydrogenation of alkenes, alkynes, and other substrates catalyzed by polymeric Pd(II) complexes of 2,3,6,7-octanetetraone tetraoxime (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1385-1390 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Coordination polymers prepared from 2,3,6,7-octanetetraone tetraoxime and bis(benzonitrile)palladium dichloride catalyzed the hydrogenation of alkenes, alkynes, carbonyl compounds, azobenzene and other substrates with some selectivity. The catalytic activity and selectivity were dependent on the palladium content in the complex.
    Additional Material: 3 Ill.
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  • 189
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    Die emulsionscopolymerisation von tetrafluorethylen mit propylen bei niedrigen temperaturen (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1429-1439 
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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: Tetrafluoroethylene and propylene were copolymerized in emulsion at low temperatures (≈25°C) by use of a redox catalyst containing ammonium peroxodisulfate, ferrous sulfate, ethylenediaminetetraacetic acid (EDTA) and hydroxymethane sulfinate. The kinetical study suggested that the working mechanism of the catalyst conforms the following scheme: where the reduction of the ferric ion seems to be rate determining (i.e. k1 ≫ k2) and the hydroxyl ion plays an important role. The overall polymerization reaction is supposed to proceed according to the Case I of the Smith-Ewart theory under the experimental conditions examined.
    Additional Material: 7 Ill.
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  • 190
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    1H and 13C NMR spectra of poly(propyl α-bromoacrylate) and poly(methyl α-bromoacrylate) (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1449-1458 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The 13C NMR spectra measured at 25 MHz of the methyl and propyl esters of isotactic and syndiotactic poly(α-bromoacrylate) were sufficiently resolved to be analysed for pentad tacticity sequences. The pentad tacticity of the syndiotactic polymers prepared with free radical initiators at -40°C agreed with those calculated for Bernoullian sequence distributions based on Pr values of 0,83-0,87. The tacticities of the isotactic polymers prepared with heterogeneous catalysts were determined on the basis of these assignments. Good internal consistency was obtained between the calculated and observed pentad proportions from the quaternary and carbonyl carbon peaks in the spectra of these polymers. The order of chemical shifts for the meso and racemic dyads and tetrads in these polymers were opposite to those found in the equivalent methacrylate polymers, but as with the latter, the 13C-T1 values were longer in the isotactic than in the syndiotactic polymers.
    Additional Material: 6 Ill.
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    Micellisation de copolymères séquencés polystyrène-polyvinylpyridinium, 3Partie 2: cf.2; les résultats présentés dans cet article font partie de la thèse d'état de J. Selb, Université L. Pasteur, Strasbourg (1978).. Influence de la concentration en sel et de la température (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1513-1524 
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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 effects of the salt concentration and temperature on the micellization phenomenon of polystyrene-poly(4-vinyl-N-ethylpyridinium bromide) block copolymers in dilute solution are investigated in solvents selective for the polyelectrolytic part (water-methanol-LiBr mixtures). The polystyrene moiety being in non-solvent media remains rather collapsed whatever temperature and salt concentration. On the contrary, the latter parameters modify strongly the conformation of the soluble polyelectrolytic chains and therefore determine the “quality” of the solvent essentially towards the polyvinylpyridinium blocks. Consequently an increase of the temperature or a decrease of the salt concentration have the same effect on the behaviour of the copolymers. In the case of a copolymer with a small molecular weight polystyrene block (Mw = 2 700), the unimer-multimer (single molecules/micelles) equilibrium is easily shifted in favour of the single molecules by increasing the temperature or decreasing the ionic strength. On the contrary, if the polystyrene moiety is longer (Mw = 6 000 - 13 000) the micellar weight of the system is little or even not at all influenced by the ionic strength and the temperature. These results emphasize that, for the investigated systems, it is the “insoluble” blocks which essentially govern the micellization phenomenon.
    Additional Material: 9 Ill.
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  • 192
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    Nuclear magnetic resonance studies on polymer carbanions, 2Part 1: cf.2.. Model compounds for α-methylstyrene and α-methylstyrene tetramer dianions (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1533-1540 
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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: 1H and 13C NMR spectra of model compounds for the poly-α-methylstyryl anion, 2-lithio, 2-potassio, and 2-cesio-2-phenylbutane, were determined. The lithium compound had a higher charge density at the α-carbon and a lower charge on the phenyl ring than the other compounds and exhibited phenyl ring rotation at higher temperatures. The activation energy was calculated to be 61, 0 kJ/mol. The potassium and cesium compounds did not show phenyl ring rotation at 80°C. Quantum chemical calculations indicated that the larger cations interact with the phenyl ring especially with the ortho carbons. 13C NMR spectra of α-methylstyrene tetramer dianion with sodium and potassium as counter cation were also measured and compared with those of the model compounds.
    Additional Material: 6 Ill.
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    Thermally initiated emulsion polymerization of styreneHerrn Prof. Dr. Ing. H. Hahn zum 65. Geburtstag gewidmet (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1553-1565 
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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 thermal polymerization of styrene in emulsion was studied by determination of the number of particles, the rate of polymerization, and the average molecular weight of the polymer formed as a function of the emulsifier concentration. For the number of particles the relation N ∼ [E]1,4 was found, whereas the rate of polymerization showed a dependence of vbr ∼ [E]0,7, only up to an emulsifier content of 0,2 mol. dm-3, but remained constant at higher concentrations. A transfer of low molecular weight radical species from the organic to the aqueous phase is discussed as a prerequisite of polymerization in the latex particles. The deviations from the Smith-Ewart theory are explained by the low rate of radical formation, which does not provide a constant radical concentration per particle.
    Additional Material: 5 Ill.
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  • 194
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    Polymerization of L-leucineN-carboxyanhydride with 1,6-hexanediamine as initiatorHerrn Prof. Dr. Dr. h.c. F. Patat zum 75. Geburtstag gewidmet (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1617-1628 
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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: L-Leucine N-carboxyanhydride was polymerized in N,N-dimethylformamide (DMF) or 1,4-dioxane (DIO) at 25°C with either 1,6-hexanediamine (1) or its monocarbamate 2 using a constant volume apparatus, initially filled with nitrogen or carbon dioxide. Number average molar masses from amino end group titrations on one hand and from initial monomer/initiator ratios and conversions on the other were practically identical for monomer conversions between 25 and 79%, indicating both the living nature of the polymerization and a participation of all initially present amino groups, despite the fact that polymer precipitation was observed at higher conversions for all systems and an additional precipitation of the carbonate 2 for the system 1/DIO/CO2 at low conversions. Two kinetic stages were observed for the latter system, but three kinetic stages for all other ones. The absence of a rapid initial polymerization period for the system, 1/DIO/CO2 as contrasted to the high initial rates for the systems 1/DMF/CO2 or 1/DMF/N2 points towards a carbamate mechanism in the first case and an amine mechanism in the second. The relation between intrinsic viscosities and number average molar masses of poly(L-leucine) in trifluoroacetic acid at 25°C was found as [η] = 0,0169 〈Mn0,86 ± 0,04 ml/g.
    Additional Material: 6 Ill.
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    Diels-Alder reaction of a trace amount of styrene with cyclopentadiene in a liquid phase (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1669-1677 
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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: With the intention to prove the possibility of applying the Diels-Alder reaction to trap a trace amount of residual styrene monomer in polystyrene, a model reaction between cyclopentadiene with styrene in a dilute o-chlorobenzene solution was carried out. In the presence of an excess amount of dicyclopentadiene, the consumption of styrene was measured with time lapse by means of gaschromatography. At temperatures ranging from 140 to 220°C, the amount of styrene was observed to decrease remarkably until it reached an equilibrium concentration. The higher the temperature was, the higher the equilibrium concentration became. The equilibrium constants at each temperature and the activation energy for the reaction were calculated.
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    HIO4-oxidized soluble polysaccharides as polyfunctional links for covalent binding of enzymes, 1. Preparation of polysaccharides and matrices for their binding (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1641-1648 
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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: Soluble hydrophillc polyaldehydes can be used as linking and crosslinking reagents for the modification and immobilization of proteins. An imine bond (or possibly an α-hydroxyamino bond) between NH2 functions of proteins or matrices and the aldehyde functions of the soluble polymer is formed under mild conditions. The polyaldehydes used were HIO4-oxidized soluble polysaccharides of different degrees of oxidation, and the NH2 matrices were Enzacryl AA and Enzacryl AH (for reference purposes also aminohexylcellulose), macroporous copolymer of glycidyl methacrylate reacted with ammonia, and nylon 6 and Estapor latices both with surface amino groups. Dextrans and Zulkowski starch were readily oxidized with HIO4, the degree of oxidation being determined by means of a modified photometric aldehyde determination method. As regards the reaction of the matrices with the polyoxidized polysaccharides (“glycosidation of the matrix”), it was found that 20 h incubation at 20°C and phosphate buffer pH = 6 furnished good results. In the investigations discussed in the present paper, relatively large quantities of polysaccharide were used for incubation, in order to achieve a high degree of glycosidation. For a closer analysis of matrices, several methods for the determination of the NH2 concentrations on matrices were examined; in this case the reaction with pentafluorobenzaldehyde in aqueous phase followed by fluoride-analysis furnished well reproducible results.
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    SynthèSe de copolymères triséquencés polybutyramide-polystyrène et polybutyramide-polyisoprène (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1695-1704 
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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 synthesis of triblock copolymers with crystalline outer blocks of polybutyramide and a central block of polystyrene or polyisoprene was performed. First polystyrene (or polyisoprene) fitted at both ends with acyllactam functions were obtained. In a second step these endstanding functions promote the lactame polymerization to yield the polyamide blocks. A careful characterization of the resulting samples was carried out. The behaviour of these block copolymers is typically that of a thermoplastic elastomer, whereby the crystalline blocks constitute the physical crosslinks in the samples.
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  • 198
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    Living anionic stereospecific polymerization of 2-vinylpyridine, 2.Part 1: cf.1. Kinetics of polymerization and nature of active centres (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1743-1750 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetic study of the propagation reaction and the viscosity measurements on solutions of active centres indicate that the living stereospecific polymerization of 2-vinylpyridine initiated by organomagnesium compounds in hydrocarbon solvents, proceeds through unsymmetrical non-aggregated ion pairs. Cryoscopic measurements on a model compound of the active centres, indicate the lack of aggregation which is attributed to the complexation of the magnesium cation by the last and the penultimate pyridine ring of the living polymer chain.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820615
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    Determination of the number-, weight-, and z-average dimensions of macromolecules by viscosity and GPC measurementsHerrn Prof. Dr. Dres. h. c. G. V. Schulz mit herzlichen Glückwünschen zum 75. Geburtstag gewidmet (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1761-1774 
    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 weight averages are calculated which have to be inserted into the Fox-Flory relationship \documentclass{article}\pagestyle{empty}\begin{document}$ {{\left[ \eta \right] = \Phi (\overline {r_{{\rm av}}^{\rm 2} } )^{{3 \mathord{\left/ {\vphantom {3 2}} \right. \kern-\nulldelimiterspace} 2}} } \mathord{\left/ {\vphantom {{\left[ \eta \right] = \Phi (\overline {r_{{\rm av}}^{\rm 2} } )^{{3 \mathord{\left/ {\vphantom {3 2}} \right. \kern-\nulldelimiterspace} 2}} } {M_{{\rm av}} }}} \right. \kern-\nulldelimiterspace} {M_{{\rm av}} }} $\end{document} if the number-, weight-, or z-average dimensions are to be determined for polymolecular polymer samples. The resulting complex molecular weight averages \documentclass{article}\pagestyle{empty}\begin{document}$ M_{r_{\rm n} } \eta _{\rm w},{\rm }M_{r_{\rm w} } \eta _{\rm w} $\end{document}, and \documentclass{article}\pagestyle{empty}\begin{document}$ M_{r_{\rm z} } \eta _{\rm w} $\en{document} are compared with simple molecular weight averages and for Schulz-Zimm and logarithmic normal distributions of the molecular weight their numerical relations to the viscosity-(Mη), number- (Mn), and weight-average molecular weight (Mw) calculated. A simple straight-forward method is outlined for the determination of the number-, weight-, and z-average dimensions of polymolecular polymers from viscosity and gel permeation chromatography measurements.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820617
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    Interaction of sodium dodecyl sulfate with poly(L-lysine) in aqueous solution (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1819-1827 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The interactions between a homopolypeptide, poly(L-lysine) [(Lys)n], and an anionic surfactant, sodium dodecyl sulfate (NaDodSO4), were studied by 13C NMR spectroscopy in D2O solution. By observing the chemical shift of the ε-amino carbon of lysine monomer in D2O solution at pH 7,3 in presence and absence of NaDodSO4, direct evidence was found for electrostatic interaction between the protonated lysine ε-amino group and the head group of the anionic surfactant. At this pH, the (Lys)n chain in NaDodSO4 solution adopts the β-form conformation and the solubility of NaDodSO4/(Lys)n complexes is too small to observe 13C-spectra. At more alkaline solutions, where the (Lys)n chain forms α-helices, the surfactant's polar group interacts with the uncharged lysyl side chain through hydrogen bonding. In the initial binding of the surfactant to (Lys)n, both the surfactant head group and alkyl chain contribute to the association with (Lys)n. With an excess of surfactant bound to α-helical (Lys)n, NaDodSO4/(Lys)n complexes show high solubility and all carbon atoms of the surfactant molecules show micelle shifts. These results suggest that the surfactant molecules form micellelike clusters around the (Lys)n helices exposing the surfactant polar head group to the medium and enhancing the solubility of NaDodSO4/(Lys)n complexes.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820621
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