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  • Electronic Resource  (3,316)
  • 1985-1989  (3,316)
  • 1920-1924
  • 1986  (3,316)
  • Polymer and Materials Science  (3,316)
  • 101
    Electronic Resource
    Electronic Resource
    A novel peptide conformation: First unequivocal observation of the oxy-analog of a β-bendThis paper is part 157 of the Linear Oligopeptides series; for part 156 see Ref. 1. (1986)
    New York : Wiley-Blackwell
    Biopolymers 25 (1986), S. 2237-2253 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The x-ray diffraction analysis of the N-benzyloxycarbonyl homo-tripeptide from α-amino-isobutyric acid has shown the occurrence of an incipient 310-helix characterized by one type-III (or type-III′) β-bend followed by one oxy-analog of the same type of β-bend. This represents the first unequivocal observation of the latter conformation, where the O - H group of the COOH moiety present at the C-terminus of the peptide main chain plays the role of the hydrogen-bonding donor. These results have been compared with those of the same peptide in its monohydrate form and of its methyl ester derivative, the x-ray diffraction structures of which are also described here.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360251203
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  • 102
    Electronic Resource
    Electronic Resource
    Synthesis of fragments by classical solution methods for use in cytochrome c semisynthesisThe amino acid residues, except glycine, are of the L-configuration. For a simpler description, the customary L-designation for individual amino acid residues is omitted. Standard abbreviations for amino acid derivatives and peptides are used according to the suggestion of the IUPAC-IUB Commission on Biochemical Nonemclature (1972) Biochemistry 11, 1726-1732. (1986)
    New York : Wiley-Blackwell
    Biopolymers 25 (1986), S. 2271-2279 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report details of the chemical synthesis of two fragments reproducing the C-terminal sequences 71-108 and 70-108 of Saccharomices cerevisiae cytochrome c. Preparation of the fragments employed classical solution methods and a fragment-condensation strategy; they have been used, together with a third fragment (sequence 67-108) [L. Moroder, B. Filippi, G. Borin & F. Marchiori (1975) Biopolymers 14, 2061-2074], in the semisynthesis of chimeric cytochromes [C. J. A. Wallace, G. Corradin, F. Marchiori & G. Borin (1986) Biopolymers 25, 2121-2132].
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360251205
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  • 103
    Electronic Resource
    Electronic Resource
    Evidence for a folded structure of met-enkephalin in membrane mimetic systems: 1H-nmr studies in sodiumdodecylsulfate, lyso-phosphatidylcholine, and mixed lyso-phosphatidylcholine/sulfatide micelles (1986)
    New York : Wiley-Blackwell
    Biopolymers 25 (1986), S. 2315-2323 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1H-nmr spectra of Met-enkephalin dissolved in aqueous solution of sodiumdodecylsulfate (SDS) micelles are reported as a function of pH and temperature. The temperature behavior of the amide protons is compared with that observed for the same peptide dissolved in aqueous solution of lyso-phosphatidylcholine (LPC) and lyso-phosphatidylcholine-sulfatide (LPC-SH) micelles. The temperature coefficients are affected by the micelle polarity, which suggests that the peptide backbone is not remote from the micelle surface. pH titration performed in the presence of SDS micelles gives a number of intrinsic and extrinsic pKa values, indicative of a folded structure of the opioid molecule. This conformation is characterized by the existence of an intramolecular hydrogen bond involving the Met-5 amide proton and an interaction of the N-terminal residue with the aliphatic side chains of both Phe-4 and Met-5.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360251209
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  • 104
    Electronic Resource
    Electronic Resource
    Helix → β conformational transition of poly(L-lysine) on dye binding (1986)
    New York : Wiley-Blackwell
    Biopolymers 25 (1986), S. 2349-2358 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Binding of an azo dye, 4′-dimethyl amino azo benzene-4-carboxylic acid (DAAC) to poly(L-lysine) (PLL) in basic aqueous solutions at 20°C has been studied. The azo dye was found to bind to PLL when its side-chain amino groups are in the uncharged state. This was found to be a cooperative phenomenon, and the binding constant and cooperativity factor have been evaluated. The binding of the dye was found to result in a conformational transition of PLL from the α-helix to the β-sheet, which in turn helps in increased dye binding.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360251212
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  • 105
    Electronic Resource
    Electronic Resource
    Concentration of protein in fibrin fibers and fibrinogen polymers determined by refractive index matching (1986)
    New York : Wiley-Blackwell
    Biopolymers 25 (1986), S. 2375-2384 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have used refractive index matching to determine the concentration of protein in the fibers in fibrin clots and of needlelike crystals of native fibrinogen. Our results are in agreement with those of Carr and Hermans [(1978) Macromolecules 11, 46-50], as determined by light scattering - namely, that protein makes up about 20% of the volume of the fiber. However, we have found that the protein concentration is strongly dependent on ionic strength. An increase in ionic strength caused a substantial drop in the protein concentration. In a buffer containing 100 mM NaCl, the protein concentration was 26.6-29.8 g of protein per 100 cm3 of polymer, and at 200 mM NaCl it was reduced to 22.1-23.1 g/100 cm3.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360251214
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  • 106
    Electronic Resource
    Electronic Resource
    Chemical synthesis of polysaccharides. 7. Enzymatic hydrolysis of (1 → 6)-α-DL-glucopyranan (DL-dextran) (1986)
    New York : Wiley-Blackwell
    Biopolymers 25 (1986), S. 1955-1965 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydrolysis of (1 → 6)-α-DL-glucopyranan (synthetic DL-dextran) by an endo-dextranase from a Penicillium species was examined in an acetate buffer solution (pH 5.3) at 37°C. Three samples of different tacticities (isotactic dyad content, 55, 63, and 72%) were employed with a clinical dextran for comparison. Colorimetric determination of the reducing end units of the saccharides produced during hydrolysis showed that the maximum degrees of hydrolysis based on the D-glucose units, (D.H.)D, for the DL-dextrans were 21.4, 27.8, and 33.0% in the order of increasing isotacitic dyad content, whereas the (D.H.)D value for the clinical dextran was 51.9%. A statistical treatment of the enzymatic hydrolysis is proposed to interpret the experimental results.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360251010
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  • 107
    Electronic Resource
    Electronic Resource
    D-Isomeric replacements within the 6-9 core sequence of ac-[Nle4]-α-MSH4-11-NH2: A topological model for the solution conformation of α-melanotropin (1986)
    New York : Wiley-Blackwell
    Biopolymers 25 (1986), S. 2029-2042 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Analogs of Ac-[Nle4]-α-MSH4-11-NH2 and Ac-[Nle4, D-Phe7]-α-MSH4-11-NH2 were prepared with D-isomeric replacements at the His6, Arg8, and Trp9 residues. The requirement for an indole moiety at position 9 also was evaluated by replacement with L-leucine in both parent fragment analogs. D-isomeric replacements at positions 6 and 8 in either series were detrimental to biological potency in frog (Rana pipiens) and lizard skin (Anolis carolinensis) in vitro melanotropic assays. However, Ac-[Nle4, D-Trp9]-α-MSH4-11-NH2 and Ac-[Nle4, D-Phe7, D-Trp9]-α-MSH4-11-NH2 were equipotent and 10 × more potent than Ac-[Nle4]-α-MSH4-11-NH2, respectively, in the lizard skin bioassay, and 30 and 1900 times more potent in the frog skin bioassay. Ac-[Nle4, D-Phe7, D-Trp9]-α-MSH4-11-NH2 was 3 × more potent than α-MSH in the frog skin bioassay. Proton nmr studies in aqueous solution revealed a marked preservation of the backbone conformation of these linear analogs. Chemical-shift variations due to the through-space anisotropic influence of the core aromatic amino acid residues permitted evaluation of side-chain topology. The observed topology was consistent with nonhydrogen-bonded β-like structure (φ = -139°, ψ = +135° for L-amino acids; φ = +139°, ψ = -135° for D-amino acids) as the predominant solution conformation. The biological and conformational data suggest that high melanotropic potency requires a close spatial arrangement of the His6, Phe7, and Arg8 side chains.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360251102
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  • 108
    Electronic Resource
    Electronic Resource
    Cytochrome c chimerae from natural and synthetic fragments: Significance of the biological properties (1986)
    New York : Wiley-Blackwell
    Biopolymers 25 (1986), S. 2121-2132 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Analogs of natural proteins have application in basic research, in medicine, and increasingly, in industry. Of the many methods developed for the fabrication of modified proteins, semisynthesis has so far been the most productive [R. E. Offord (1983) Proc. Eur. Peptide Symp., 17 31-42]. The technique of fragment-condensation semisynthesis takes as its basic raw material the native protein; fragments derived from it are manipulated by sequential degradation and resynthesis before recombination. While gene manipulation may overtake protein manipulation in general usefulness, certain types of analogs will remain accessible only by semisynthesis. Fragment condensation semisynthesis, as described above, has been used in preparing cytochrome c analogs [C. J. A. Wallace (1979) Proc. Am. Peptide Symp. 6, 609-612]. To overcome the difficulty of replacing amino acids far from convenient cleavage sites, a number of variants of the method have also been used. These include fragment-specific chemical modification [C. J. A. Wallace & K. Rose (1983) Biochem. J. 215, 651-658] and solid-phase synthesis of small [P. J. Boon, G. I. Tesser, H. H. K. Brinkhof & R. J. F. Nivard (1981) Proc. Eur. Peptide Symp. 16, 127-130] or large fragments [L. E. Barstow, R. S. Young, E. Yakali, J. J. Sharp, J. C. O'Brien, P. W. Berman & H. A. Harbury (1977) Proc. Natl. Acad. Sci. USA 74, 4148-4250]. The latter study gave low final recoveries, so we have prepared large peptides (38-42 residues) by classical solution methods. We have examined both their use in the reformation of the complete protein, and the physical and biochemical properties of the product analogs compared with those of the native proteins.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360251107
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  • 109
    Electronic Resource
    Electronic Resource
    The effect of monovalent cations on the association behavior of guanosine 5′-monophosphate, cytidine 5′-monophosphate, and their equimolar mixture in aqueous solution (1986)
    New York : Wiley-Blackwell
    Biopolymers 25 (1986), S. 2149-2172 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1H- and 31P-nmr spectroscopy have been used to investigate the self-association of M2(5′-CMP) [M = Li+, Na+, K+, Rb+, or (CH3)4 N+; 5′-CMP = cytidine 5′-monophosphate], the self-association of Li2(5′-GMP) (5′-GMP = guanosine 5′-monophosphate), and the heteroassociation of 5′-GMP and 5′-CMP (1 : 1 mole ratio) in aqueous solution as a function of the nature of the monovalent cation. Proton spectral differences for the different 5′-CMP salts exhibit a cation-size dependence and have been ascribed to a change in the stacking geometry. An average stacking association constant of 0.63 ± 0.24M-1 at 1°C, consistent with the weak stacking interactions of the cytosine bases, was determined for the 5′-CMP salts. Heteroassociation of 5′-GMP and 5′-CMP follows the reverse of the cation order for the formation of ordered aggregates of 5′-GMP. Heteroassociation occurs in the presence of Li+, Na+, and Rb+ ions, but only self-association occurs for the K+ nucleotides. Li2(5′-GMP), which does not form ordered species, self-associates to form disordered base stacks with a stacking constant of 1.63 ± 0.11M-1 at 1°C.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360251109
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  • 110
    Electronic Resource
    Electronic Resource
    Structural investigation of poly-L,D-proline, a synthetic ion channel across bilayer membranes: Crystal structure and molecular conformation of two tetra-D,L-proline derivatives (1986)
    New York : Wiley-Blackwell
    Biopolymers 25 (1986), S. 2227-2236 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structures and molecular conformations of two tetraproline derivatives with alternating configurations Boc(D-Pro,L-Pro)2OH and Boc(D-Pro,L-Pro)2OCH3 are investigated in connection with the ability of the homologous polymer to selectively increase (as an ion channel) the ion permeability across bilayer membranes. Both tetramers are characterized by the cis-trans alternating conformation of the peptide bonds, which formally transforms in a turn of the poly-D,L-proline channel after a cis-trans change of the central peptide residue.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360251202
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  • 111
    Electronic Resource
    Electronic Resource
    Sol-sol structural transition of aqueous agarose systems (1986)
    New York : Wiley-Blackwell
    Biopolymers 25 (1986), S. 2255-2269 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A structural transition is reported to occur in aqueous sols of agarose, an electrically uncharged biostructural polysaccharide. The transition has no measurable effect on size dispersity on the shape of the solute polysaccharide as observed by precision photon correlation spectroscopy. It originates a low-angle pattern of scattered light similar to that which monitors phase separations in polymer blends. Thus, it must be due to some extent to spatially modulated polymer clustering, typical of spinodal decomposition. In the interval of temperatures studied, it precedes very distinctly in time the thermoreversible sol-gel transition, which is known to be promoted at higher concentrations. It also anticipates to an appreciable extent the spatial density modulation observed in the gel. Although reported here for the first time, a spinodal decomposition of the sol that precedes and possibly triggers the processes leading to gelation does not come unexpectedly in terms of site-bond correlated-percolation theory. In general, this occurrence raises the question as to whether the spontaneous onset of regions of higher and lower polymer concentration (spinodal separation) may be regarded as a novel path for biomolecular interactions and the self-assembly of order in biomolecular systems.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360251204
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  • 112
    Electronic Resource
    Electronic Resource
    Energy transfer in polynucleotide homopolymers and copolymers (1986)
    New York : Wiley-Blackwell
    Biopolymers 25 (1986), S. 2309-2313 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the fluorophore Tb3+ as a reporter, the effect of thallium (Tl+1) on the transfer of energy in polyribonucleotides and polydeoxynucleotides at room temperature has been studied. In p(G), p(G, I), and pd(G)6 thallium greatly increases the transfer of uv energy absorbed by the bases to Tb3+. In DNA, p(G, U), p(G, A), p(A, U), p(X), p(A), p(U), p(I), pd(G, A)6, and pd(G, T)5 thallium has little or no effect. Thallium increases intersystem crossing to the triplet states only in p(G), p(G, I), and pd(G)6, and the triplets overlap the excited singlet state in Tb3+. In those G- and X-containing polymers showing little thallium effect, the evidence suggests that intersystem crossing is comparatively high to begin with. These polymers, including DNA, appear to transfer absorbed energy to triplet states efficiently at room temperature.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.360251208
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  • 113
    Electronic Resource
    Electronic Resource
    Comparisons among some tetraalkoxysilanes in the hydrolytic precipitation of silica into elastomeric networks (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2861-2866 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Four tetraalkoxysilanes Si(OR)4 were absorbed into networks of polydimethylsiloxane and then hydrolyzed, using a variety of catalysts, to give reinforcing silica particles. On the basis of the amount of silica precipitated and the extent of reinforcement, the (decreasing) order of effectiveness was found to be tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and tetramethoxysilane.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021871213
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  • 114
    Electronic Resource
    Electronic Resource
    Thermodynamics of gas solubility in polymeric liquids (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2867-2882 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A modified fluid-lattice model for mixtures of fluids is presented. Expressions for the basic thermodynamic quantities of mixing are given. From the equation for vapor-liquid equilibrium, the expression for the Henry constant at low pressure is derived. Weight fraction Henry constants for gas-polymer and gas-polymer-polymer systems are derived as limiting cases. Predictions of theory about the effect of temperature on the Henry constants are compared with experimental data for twenty two polymer-organic vapor systems. In almost all cases the Henry constants are reproduced within the limit of experimental error. The effect of pressure on gas solubilities is considered. The effect of polymer-polymer binary interaction parameter on the Henry constant in a gas-polymer-polymer mixture is also discussed.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021871214
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  • 115
    Electronic Resource
    Electronic Resource
    Lyotropic mesophase of imogolite, 1. Effect of polydispersity on phase diagram (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2883-2893 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The acidic aqueous solution of imogolite is proposed to be an ideal lyotropic system. No temperature dependence was marked on the two phase boundary concentrations (A and B points) of imogolite solutions as predicted by the theories of Flory and Onsager. A satisfactory quantitative agreement was observed with Onsager's theory. The polydispersity of rod lengths was found to shift the A point towards lower concentrations than expected from theory.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021871215
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  • 116
    Electronic Resource
    Electronic Resource
    Lyotropic mesophase of imogolite, 2Part. 1: cf.7.. Microscopic observation of imogolite mesophase (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2895-2907 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Imogolite, though achiral, forms cholesteric spherulites in the anisotropic phase as shown by the regular striations arranged in a swirl-like or fingerprint pattern observed through a polarizing microscope. Electron microscopy revealed the raft-like imogolite sheet floating in the anisotropic phase. The structure of the imogolite sheet was deduced from periodicities observed by an electron microscope using various imaging conditions. The origin of the twisting force to maintain the cholesteric ordering is also discussed.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021871216
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  • 117
    Electronic Resource
    Electronic Resource
    Synthesis of liquid crystalline polyacrylates and their use in capillary gas chromatography (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1407-1414 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: New enantiotropic liquid crystalline compounds based on 4-(p-substituted phenylazo)phenol and m-cresol esters containing an acryloyloxy group were synthesized. Polyacrylates were prepared from these monomers by radical polymerization. The resulting polymers exhibit nematic enantioropic properties. The polyacrylates have broader nematic ranges and higher nematic to isotropic transition temperatures as compared to their corresponding monomers. The nematic range is dependent on both the lateral substituents and the terminal substituents. The laterally substituted polyacrylates gave a narrower nematic range than unsubstituted compounds. Increase in carbon number in the terminal alkyl group leads to a broader nematic range. The liquid crystalline polyacrylates could be coated uniformly on the inside of a glass capillary tubing. The coated capillary columns show an excellent selectivity in gas chromatography for the separation of isomeric compounds. The liquid crystalline stationary phases are highly stable up to 230°C without column bleeding.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870609
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  • 118
    Electronic Resource
    Electronic Resource
    Syntheses of telechelic oligo- and poly(carboxypiperazine)s (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1415-1422 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(carboxypiperazine) is only accessible via low temperature polycondensation methods. The melting point of the polymer is higher than the temperature of its decomposition. Oligomers with piperidine end groups were prepared to determine the melting points of the pure polymer by extrapolation from the melting points of the oligomers. The decomposition temperatures were determined by thermogravimetry. These studies led to the design of meltable telechelics.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870610
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  • 119
    Electronic Resource
    Electronic Resource
    Dégradation contrôlée des polyisoprènes-1,4 par le couple phénylhydrazine/oxygène, 3Part 2: cf.1.. Molécules modèles de structures phénylhydrazone conjuguées (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1573-1582 
    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 identify phenylhydrazone structures in the reaction products of oxidized polyisoprene or its models with phenylhydrazine, the UV, 1H NMR, 13C NMR and MS spectra as well as the steric exclusion chromatography parameters were determined for phenylhydrazones derived from aldehydes and ketones, selected as models of conjugated carbonyl structures, which could result from the oxidation of polyisoprene units. By comparison with possible coexistent structures, inclusively phenylhydrazones of non-conjugated carbonyl derivatives, oxidized polyisoprene structures can be identified.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870701
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  • 120
    Electronic Resource
    Electronic Resource
    Phase structure and compatibility studies in poly(ethylene oxide)/poly(methyl methacrylate) blends (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1557-1571 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Morphology, crystallinity, and melting behaviour of solution-cast films of poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA) blends were investigated as a function of composition, using optical and scanning electron microscopy, differential scanning calorimetry, and dilatometry. Up to a content of about 40 wt.-% of PMMA the blend films are completely filled with PEO spherulites, no separated domains of PMMA being observed. This observation suggests, in agreement with small angle X-ray scattering analysis, that for such compositions the PMMA molecules are incorporated in interlamellar regions of PEO spherulites. Blends with higher content of PMMA show islands of crystalline PEO within a matrix of PMMA; large amorphous regions coexist with not well developed PEO spherulites. Addition of PMMA strongly increases the nucleation density for PEO crystals. The solubility parameters δ of PEO and PMMA were calculated from specific volume values as a function of temperature. It was found that at temperatures higher than that of PEO melting the difference δ(PEO) - δ(PMMA) is very low suggesting that the two polymers are compatible in the melt. Compatibility of PEO and PMMA was also predicted by using a theoretical approach which allows to calculate the free energy of mixing as a function of composition and temperature.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870625
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  • 121
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    A novel synthesis of polystyrene macromonomers (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1583-1591 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Lithium diisopropylamide (2) was found to undergo a metalation reaction with 4-methylstyrene (1) to form 4-vinylbenzyllithium (3), but to induce neither addition reaction nor vinyl polymerization. The equilibrium constant between 2 and 3 in THF was calculated to be 0,54 at 20°C. The 4-vinylbenzyllithium formed initiates the polymerization of styrene derivatives to form oligomers. The resulting oligomers have a polymerizable vinyl group at the chain end quantitatively and can be regarded as a “macromonomer”. Synthesis of polystyrene, having a primary amino group at the chain end, was carried out through the reaction of polystyrene macromonomer with N-methylethylenediamine. More than 97% of polystyrene were aminated within 6 h reaction.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870702
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  • 122
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    The copolymerization of maleic anhydride with propene and isobutene (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1593-1596 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Alternating copolymers were obtained by radical copolymerization of propene (Pr) and isobutene (IB) with maleic anhydride. Both polymers (Pr and IB) do not homopolymerize under the applied reaction conditions. The copolymerization rates were determined.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870703
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  • 123
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    Kinetics of the copolymerization of styrene with maleic anhydride in ethyl methyl ketone (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1597-1602 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The copolymerization of styrene and maleic anhydride in ethyl methyl ketone as solvent and with benzoyl peroxide as initiator at 60-80°C in the entire feed composition range was studied. The resulting copolymers appear to have negative and positive deviations from alternation as determined by use of elemental analysis. The experimental data were found to fit a three-reactivity-ratio copolymer composition equation from the penultimate model. The inclusion of the reactivity ratio, kSM (=kSMM/kSMS), in addition to rSS (=kSSS/kSSM) and rMS (=kMSS/kMSM), allows prediction of a positive deviation from the alternation, i.e. the mole fraction of maleic anhydride in the copolymer being higher than 0,5.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870704
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  • 124
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    Kinetics of the free radical copolymerization of diethyl maleate with styrene (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1713-1726 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The free radical copolymerization of diethyl maleate (M1) with styrene (M3) was studied in bulk at 60°C with azoisobutyronitrile as initiator. In order to compute the reactivity ratios, we determined the copolymer composition by microanalysis of the carbon content. The evaluation of the data was carried out according to two procedures; the Kelen-Tüdös linearization method and the non-linear least-squares of Tidwell and Mortimer. The ratios obtained with the latter, r13 = 0,001 and r31 = 6,592, yielded a better fit. Different kinetic models were tested to describe the observed dependence of reaction rate on monomer mixture composition. The experimental results could be successfully described according to a kinetic model that assumes diffusion control of the termination reaction. The resulting kinetic equation contains two parameters whose values were determined from the experimental copolymerization rates. The value of one of these parameters could be obtained also from homopolymerization data for styrene. This proves that the parameters have physical significance and are not arbitrary quantities chosen to fit the experimental results.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870715
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  • 125
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    Rheological properties of liquid-crystalline side-group polymers in the isotropic, nematic, and smectic states (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1727-1736 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melt viscosity of seven liquid-crystalline side-group polymers with polyacrylate and polysiloxane main chains is measured as a function of shear rate and temperature. In the isotropic and also in the nematic phase none or only a very small dependence of the melt viscosity on shear rate is observed for the shear rates investigated. The melt viscosity in the nematic phase is higher than that in the isotropic phase. This is contrary to the results for liquid crystalline mainchain polymers and points to the fact, that there is no resulting orientation in shear flow of liquid-crystalline side-group polymers in the nematic phase. In the smectic phase the melt viscosity is very high and strongly shear-rate dependent. These results are compared with dielectric relaxation measurements on polymethacrylates and a polychloroacrylate.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870716
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  • 126
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    The effect of TiBr4 on ethylene polymerization catalyzed by tetrabenzyltitanium (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1737-1744 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the ethylene polymerization catalyzed by Ti(CH2C6H5)4/TiBr4 in toluene at 0°C was studied. The effects of the mole ratio of the catalyst components and of the quantity of catalyst on the polymerization were investigated. Using the number of active centres, the rate constant of the propagation reaction was evaluated. The number of active centres was determined by quenching the polymerization with 1-butanol tritiated at the hydroxyl group. Compared with the kinetic data of the catalyst system Ti(CH2C6H5)4/AlBr3, the present results indicate that the nature of the cocatalyst mainly affects the conditions for the formation of active centres, but has no essential influence on their reactivity. These results support the concept of monometallic structure of the active centres in Ziegler-Natta catalysts.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870717
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  • 127
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    Viscosity of aqueous and alkaline solutions of poly(ethylene oxide) (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1745-1755 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Viscosity measurements over a wide range of temperature were made on aqueous solutions of poly(ethylene oxide) samples of different molar mass and of low polydispersity. Above ca. 308 K the Mark-Houwink exponent decreases and tends to a value of 0,50 at a lower critical solution temperature of 376 ± 2 K. The same value for this θ-temperature is derived also as that at which the slope of Stockmayer-Fixman plots tends to zero. At 298 K the unperturbed dimensions [〈r2〉0/M]1/2 = 0,089 nm · g-1/2 · mol1/2 and their temperature coefficient d ln 〈r2〉0/dT ≈ - 1,5 (±0,5) · 10-3 K-1. In aq. KOH the intrinsic viscosity [η] is virtually uninfluenced by pH at low-medium pH, but at high pH, [η] falls sharply. Viscosity and phase separation measurements yield θ-conditions in 1,24 M aq. KOH at 298 K. The derived polymer-water interaction parameters χ increase from 0,449 at 276 K to 0,493 at 358 K, but the enthaplic component χH is incapable of yielding a meaningful value for the solubility parameter δ2 of the polymer in such a hydrogen-bonding system. The calculated value of χ2 was 18,9 (kJ · dm-3)1/2.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870718
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  • 128
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    Epitaxial polymerization of acetylene (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1757-1764 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Epitaxial polymerization of acetylene was studied using systematic series of homologous isomorphic compounds as substrates for the purpose of establishing techniques for preparing well oriented polyacetylenes. From electron microscopy, it was confirmed that polyacetylenes grow on the substrate in the form of fibrils whose orientation is strongly dependent on the lattice matching between polyacetylene and substrate crystals: e.g. with naphthalene and anthracene as substrates the fibrils assume zigzag orientation in three specific directions on the crystal but with biphenyl and terphenyl the zigzag fibrils assume predominantly two specific directions. The mechanism of epitaxial growth during polymerization on the various substrates is discussed on the basis of the features of the epitaxial fibrils.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870719
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  • 129
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    Kinetics of radical polymerization of methyl methacrylate initiated with dimethyl 2,2′-azodiisobutyrateDedicated to Professor Dr. Dr. h. c. mult. G. V. Schulz on the occasion of his 80th birthday (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1765-1775 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of free-radical bulk polymerization of methyl methacrylate with dimethyl 2,2′-azodiisobutyrate as an initiator was investigated at 40, 60, and 80°C. Non-ideal polymerization behaviour was observed when the initiator concentration was varied by a factor of more than one thousand. This departure from classical polymerization kinetics is discussed in terms of primary radical termination and a chain length dependent termination rate constant, with the structural similarity of both primary and polymeric radicals facilitating the treatment very much. The kinetic analysis indicates that in the polymerization of methyl methacrylate the termination rate constant is a function of the degree of polymerization of the involved macroradicals.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870720
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  • 130
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    Calculation of the integral chemical distribution of block copolymersDedicated to Dr. Gerhard Fritz on the occasion of his 60th birthday (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1777-1786 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Calculations show for an anionic block copolymerization under ideal conditions that the integral chemical distribution of a block copolymer (with given number-average molar mass and average chemical composition) should be independent of the number of blocks in the copolymer and thus independent of the way in which the monomers are added during polymerization. Calculations for block copolymers consisting of styrene and butadiene are given to illustrate the decrease of the width of the chemical distribution with increasing molar mass. The chemical distributions of styrene-butadiene block copolymers determined experimentally by successive fractional demixing with demixing solvents are consistently broader than the calculated ones. This must be attributed to association equilibria of the initiator and of the living polymer chains and also to termination reactions of the polymer chains. The theoretically expected narrow chemical distributions can be obtained approximately by head and tail fractional demixing of the copolymers with demixing solvents.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870721
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  • 131
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    Dynamic mechanical behaviour and phase separation of mixtures of polysulfone with bis[4-(4-ethynylphenoxy)phenyl]-sulfone or poly(phenylene sulfide) (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1787-1799 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic mechanical behaviour and microphase-separation structure of polysulfone blends with bis[4-(4-ethynylphenoxy)phenyl]sulfone and with poly(phenylene sulfide) were investigated using torsional braid analysis and scanning electron microscopy. The experimental results showed that the size and shape of dynamic mechanical damping peaks and the structure characteristics of polysulfone blends with sulfur-containing polymers do not only depend on the chemical and physical nature and the weight fractions of the two components but also on conditions of thermal treatment leading to cross-linking reactions. In these multi-component polymer systems, the initially compatible mixture turns into an incompatible two-phase system during heating.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870722
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  • 132
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    Shrinkage force and molecular orientation in polyacrylonitrile fibersDedicated to Prof. Dr. Dres. h. c. G. V. Schulz on the occasion of his 80th birthday (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1801-1806 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A correlation between sonic modulus and shrinkage force was found for fibers spun from copolymers of acrylonitrile and other vinyl monomers. Using this correlation, the orientation factor as defined by Moseley can be calculated from a single shrinkage force measurement, permitting a fast and reliable characterization of fibers and spinning conditions. Equipment and modus operandi are described.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870723
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  • 133
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    Reactivity of N-alkylated cyclic iminoether salts having vinyl groups, 2Part 1: cf.9. Polymerization and copolymerization of 2-isopropenyl-3-methyl-2-oxazolinium salts (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1807-1817 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 3-Methyl-2-isopropenyl-2-oxazolinium salts (4a, b) were prepared by alkylation of 2-isopropenyl-2-oxazoline (2). Their preparation is much easier than that of their vinyl analogues, 3-methyl-2-vinyl-2-oxazolinium salts, which cannot be isolated due to their high tendency to polymerization. 4a, however, was found, to show a low tendency toward radical and anionic polymerization, but it can be smoothly radically copolymerized with some vinyl monomers. The copolymerization parameters of 4a were determined and discussed in comparison with those of 2.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870801
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  • 134
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    Photochimie des polyamides aliphatiques, 5Partie 4: cf.18. Oxydation du polydodécanamide (PA12) photocatalysée par TiO2 et ZnO (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1819-1832 
    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 two photoactive pigments (ZnO and TiO2 in the rutile form) on the dual photochemistry occurring in polydodecanamide was analyzed, on analytical and kinetics grounds. Variations in the concentration of amino, hydroperoxide and imido groups as function of the photoactive pigment content were studied. At wavelengths longer than 300 nm, zinc oxide exhibits an inner filter effect at low content; an antagonist photocatalytic influence is observed at high content (5-10%). The inner filter effect and the photocatalytic activity of titanium dioxide are observed simultaneously even at low content of titanium dioxide (1-10%). At 254 nm and 25°C, the filter effect of ZnO is prevalent on the formation of amino and acidic groups. Titanium dioxide acts as a filter and a photocatalyst: the formation of amino groups is inhibited, whereas the rate of formation of acidic groups is apparently not modified.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870802
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  • 135
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    Preparation and thermolysis of N-ammonioamidates as model precursors of new type of segmented poly(ether-urethane)s (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1833-1841 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: N-Ammonioamidates 2 (aminimides) containing a hydroxyl group, oxyalkylene units, and an alkylene chain or a phenylene group in an acyl moiety were prepared in satisfactory yields from the corresponding esters 1. By thermolyses in diglyme, cyclic urethanes (type of crown ethers) 3 and oligo(ether-urethane)s 4 were formed, depending on the structure of the N-ammonioamidates. The latter are applicable to the syntheses of new model compounds of segmented poly-(ether-urethane)s.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870803
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  • 136
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    Photodimerization and photopolymerization of amphiphilic cinnamic acid derivatives in oriented monolayers, vesicles and solution (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1843-1853 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cinnamic acid moieties were incorporated into amphiphilic compounds containing one and two alkyl chains. These lipid-like compounds with photoreactive units undergo self-organization to form monolayers at the gas-water interface and bilayer structures (vesicles) in aqueous solutions. The photoreaction of the cinnamic acid moiety induced by 254 nm UV light was investigated in the crystalline state, in monolayers, in vesicles and in solution in organic solvents. The single-chain amphiphiles undergo dimerization to yield photoproducts with twice the molecular weight of the corresponding monomers in organized systems. The photoreaction of amphiphiles containing two cinnamic acid groups occurs via two mechanisms: The intramolecular dimerization produces bicycles, with retention of the molecular weight of the corresponding monomer. The intermolecular reaction leads to oligomeric and polymeric photoproducts. In contrast to the single-chain amphiphiles, photodimerization processes of lipoids containing two cinnamic acid moieties also occur in solution in organic solvents.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870804
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  • 137
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    Réaction époxide amine: Réactivité du sulfonyl-4,4′ dianiline vis-à-vis du groupement époxy (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1855-1869 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanism and kinetics of the polycondensation of 4,4′-sulfonyldianiline (2) with 2,3-epoxy-1-phenoxypropane (1) were analysed in the absence or presence of a catalyst [N,N-(dimethyl)-benzylamine or BF3 complex]. Chemical data obtained by 13C NMR and HPLC show that secondary reactions (homopolymerisation, reaction of hydroxyl groups with the epoxy groups) take a prominent part.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870805
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  • 138
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    Coordination polymers of N,N′-bis(8-hydroxy-5-quinolinyl)-terephthalamide (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1871-1875 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes of the bisbidentate ligand N,N′-bis(8-hydroxy-5-quinolinyl)terephthalamide (1) were synthesized. All the metal complexes are characterized by elemental analyses, infrared spectra, electronic reflectance spectra, magnetic susceptibility measurements and thermogravimetry. All the complexes showed a polymeric nature with a octahedral stereochemistry at the coordinated metal atom. The fungicidal screening of the coordination polymers showed them to be antifungal against Penicillium islandicum, Rizopus nigricans and Botrydiplodia theobromae.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870806
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  • 139
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    Synthesis of novel ordered poly(ester-amide)s (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1-7 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Five different completely aromatic, ordered poly(ester-amide)s 6a  -  e were prepared from diphenols 5 and 4,4′-carbonyliminodibenzoyl dichloride (3). This bifunctional “amide-acid chloride” was synthesized in two steps by oxidation of 4,4′-dimethylbenzanilide (1) with permanganate under neutral conditions and subsequent reaction with thionyl chloride. The polymers obtained were characterized by IR spectroscopy and viscosity measurements. Their physical properties like density, solubility, and thermal behaviour were also studied.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870101
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  • 140
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    Polymers with tertiary amino groups obtained by the reaction between chloromethylated polystyrene and 3-alkylaminopropionitrile (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 9-22 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymers with tertiary amino groups were obtained by reaction of chloromethylated polystyrene (CMPS) with 3-alkylaminopropionitriles (2a  -  e). The resulting polymers 3a  -  e were characterized by elemental analyses, IR and 1H NMR spectra. Kinetic investigation showed that the reaction is characterized by two rate constants, the rate change taking place at a conversion of 45-50%. Viscosimetric studies of the hydrochlorides of polymers 3a  -  e in water and methanol showed that they behave as polyelectrolytes only in methanol. The abnormal behaviour of water solutions was explained by hydrolysis reaction. To prove the conclusions on the molecular structures of 3a  -  e and the reactivity of CMPS, a study of the reaction of benzyl chloride with the same amines was performed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870102
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  • 141
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    Some spectral and thermal contributions to the curing of new epoxy compounds with aromatic diamines (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1907-1914 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The curing reaction of the new bis(2,3-epoxypropyl) 4,4′-carbonyldi-ω-phthalimidoalkanoates 1a-c was studied with several aromatic diamines 2a-c as curing agents. The process was followed by means of spectrophotometric techniques. The influence of the nature of the curing agent on the reaction rate was examined. The adduct formation yielding first chain extension, is the first step of the reaction, followed by crosslinking, once the gel point has been reached. The products obtained were found to be rather thermostable.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870810
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  • 142
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    Liquid crystalline elastomers based on liquid crystalline side group, main chain and combined polymersPresented in part at the: 2nd Macromolecular Symposium, BRD-USSR, 30. 9.-4. 10. 1985, Mainz, West Germany; cf.6. (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1915-1926 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Covalently crosslinked liquid crystalline networks with elastic properties were prepared in isotropic solution from linear liquid crystalline polymers. As linear precursors for the networks were used: (i) polymers with the mesogenic groups in the side groups (polyacrylates and polymethacrylates), (ii) polymers with the mesogenic groups in the main chain (polymalonates) and (iii) polymers with the mesogenic groups in main chain and side groups (“combined liquid crystalline polymers”). In all crosslinked polymers the liquid crystalline phases of the linear polymers are retained. For low degrees of crosslinking (≤2 mol-%) the phase transition temperatures remain nearly unchanged. These elastomers are very soft above Tg and can be easily stretched for more than 100%. For higher degrees of crosslinking the phase transition temperatures are reduced.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870811
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  • 143
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    Radical polymerization of methyl methacrylate and methyl acrylate in the presence of an oligomer of 2-methoxy-4-vinylphenol (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1945-1952 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Methyl methacrylate (MMA) and methyl acrylate (MA) were polymerized in the presence of an oligomer of 2-methoxy-4-vinylphenol (OMVP) with a double bond at its end. It is shown by means of the UV spectra and the kinetic treatment that the double bond disappears by hydrogen transfer from the growing polymer chain to OMVP and that the OMVP radical formed propagates further. In the polymerization of MMA, the transfer rate is comparable with the termination rate if [OMVP] ≤ 0,52 mol · 1-1. In the polymerization of MA, the transfer rate is very much higher than the termination rate for [OMVP] ≥ 0,016 mol · 1-1. It is suggested that each PMA chain carries one OMVP unit at the end.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870813
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  • 144
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    Synthesis of linear poly(4-vinylbenzaldehyde) by means of anionic living polymerization of 1,3-dimethyl-2-(4-vinylphenyl)imidazolidine and subsequent hydrolysis (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 141-147 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(4-vinylbenzaldehyde)s (4) of known chain lengths and of narrow molecular weight distributions (M̄w/M̄n ≈ 1,1) were synthesized by means of anionic living polymerization of 1,3-dimethyl-2-(4-vinylphenyl)imidazolidine (1) with oligo[α-methylstyryl]potassium (2) and subsequent acid hydrolysis to remove the imidazolidine protective group. The living polymer of 1 can initiate further polymerization of α-methylstyrene, resulting in the preparation of a triblock copolymer of the type poly[α-methylstyrene-b-(4-vinylbenzaldehyde)-b-α-methylstyrene] in quantitative yield after hydrolysis.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870113
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  • 145
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    Composition-properties relationships in propene-ethene random copolymers obtained with high-yield Ziegler-Natta supported catalysts (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1927-1943 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization and thermal behaviour of crystallizable random propene/ethene copolymers (P-co-E) was systematically investigated. Index of crystallinity and, index of γ-form, enthalpy and entropy of fusion, equilibrium melting temperature, spherulite growth rate, and overall kinetic rate constant were determined and correlated with the overall ethene content and with the concentration of specific chemical defects as determined by 13C NMR analysis (PEP, EPP, EPE triads). The samples of the copolymers, obtained with very-high-yield Ziegler-Natta catalysts, were characterized by IR, 13C NMR, wide angle X-ray scattering, and differential scanning calorimetry.
    Additional Material: 16 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870812
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  • 146
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    Hydroxytelechelic polybutadiene, 9Part 8: M. El. Ghafari, Q.-T. Pham, Y. Camberlin, Makromol. Chem. 186, 2383 (1985). Kinetics of reactions in solution and in bulk between radically obtained hydroxytelechelic polybutadiene and propyl and phenyl isocyanate studied by 1H NMR (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1963-1976 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the reactions of radically obtained hydroxytelechelic polybutadiene (Arco R45M) with propyl isocyanate and phenyl isocyanate were studied by 1H NMR at high field. The reactivities of the three alcohol functions of Arco R45M were found to be different. The three individual reactions follow a 3rd order law and are accelerated by autocatalysis. There is competition between (OH, OH) auto-association and (free OH + isocyanate) reactions. As a consequence, rate constants are strongly affected by (OH, OH) association phenomena.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870815
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  • 147
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    Aqueous polymerization of vinyl monomers in the presence of surfactants, 3Part 2: cf.18. System: Acrylamide/poly(butyl acrylate) latex (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 257-262 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the polymerization of acrylamide initiated by potassium peroxodisulfate in aqueous medium is studied in the presence of poly(butyl acrylate) latex. The rate of acrylamide polymerization increases with the concentration of the latex in the reaction system. The increase is especially pronounced at concentrations of solid latex higher than 100 g per dm3 of polymerization mixture. The activation energy of the acrylamide polymerization in the presence of poly(butyl acrylate) latex is 85,8 kJ · mol-1. This value is substantially higher than the value of 70,7 kJ · mol-1 found for the activation energy of the polymerization of acrylamide in the absence of poly(butyl acrylate) latex. A set of reactions is proposed and the equation describing the simultaneous homopolymerization of acrylamide and grafting of poly(butyl acrylate) latex with acrylamide is derived.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870202
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  • 148
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    Two-Phase(water/organic) free radical polymerization of water-soluble vinyl monomers using lipophilic acylated β-cyclodextrins as initiator carrier (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 263-271 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The acylated β-cyclodextrins, heptakis(2,3,6-tri-O-acetyl)-β-cyclodextrin, heptakis(2,3,6-tri-O-obutyryl)-β-cyclodextrin, heptakis(2,3,6-tri-O-butyryl)-β-cyclodextrin, and heptakis(2,3,6-tri-O-pivaloyl)-β-cyclodextrin, cause a marked increase in the rate of polymerization of water- soluble vinyl monomers using water insoluble initiators in the two-phase system consisting of water and an organic solvent (chloroform/ligroin, volume ratio 1 : 4). A plausible mechanism for this polymerization is proposed: The lipophilic acylated cyclodextrin acts as an initiator carrrier from the organic to the aqueous phase where polymerization takes place.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870203
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  • 149
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    Structure of 2,2,5,5,6,6,9,9-octamethyl-2,5,6,9-tetrasiladecane, a structural precursor of poly[(tetramethyldisilanediyl)ethylene] (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2011-2017 
    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 obtain information for suggesting the most likely molecular and crystal structure of poly[(tetramethyldisilanediyl)ethylene] (PTMDSE) an X-ray study of the structural precursor 2,2,5,5,6,6,9,9-octamethyl-2,5,6,9-tetrasiladecane (TSD) is carried out. The TDS molecule is centrosymmetric, the CSiCCSiSiCCSiC chain having an almost planar all-trans conformation. In the crystal of TSD one can distinguish molecular layers parallel to the a b plane; the long axes of the TSD molecules form an angle of 24,4° with the layer plane; intermolecular contacts in layers are shorter, on the average, than interlayer contacts.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870819
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  • 150
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    Block copolymers with controlled interphase width. Effects of interphase and composition on domain dimensions (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2019-2037 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ultrathin osmium tetroxid stained sections of solution cast block copolymer films were studied by electron microscopy. Two morphological systems were prepared from diblock copolymers containing 80 wt.-% styrene and 20 wt.-% isoprene: Systems with asymmetric lamellar morphology cast from cyclohexane, a preferential solvent for PI; and spherical morphology of rubber spheres in a continuous PS matrix, cast from tetrachloromethane, a non-selective solvent. For the two morphologies the variation of domain dimensions was studied in dependence of molecular weight in the range from 70 000 to 600 000 g/mol. Two types of block copolymers were investigated: Unmodified block copolymers and block copolymers containing 10 wt.-% of a random interblock between the pure polystyrene and polyisoprene blocks. For both kinds of morphologies the domain dimensions of the unmodified systems vary with Mn2/3 as predicted by Helfand's theory. In the modified block copolymers a much weaker increase with Mn is found for both morphological systems. The results can be understood in terms of equilibrium domain dimensions controlled by an interfacial tension depending on both composition and sequence structure of the block copolymers.
    Additional Material: 13 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870820
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  • 151
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    Synthesis of high-molecular-weight polysuccinamides by polycondensation of active succinates with diamines (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2053-2062 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: High-molecular-weight, film- and fiber-forming polysuccinamides were synthesized by polycondensation of active diesters of succinic acid with hexamethylenediamine or dodecamethylenediamine under mild conditions. By kinetic investigations it was established that the formation of high-molecular-weight polysuccinamides is connected with a low rate of chain-terminating formation of a cyclic imide and its nearly complete suppression by chain-growth aminolysis reaction.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870902
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  • 152
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    Transformation of oligodimethylsiloxanols in the presence of a strong base. Reactivity enhancement of the siloxane bond by the adjacent hydroxyl group (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2039-2052 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the base catalysed disproportionation of polydimethylsiloxanes having silanol end groups was studied using the model systems 1,1,3,3,3-pentamethyldisiloxane-1-ol (1) and 1,1,3,3,5,5,7,7,9,9,9-undecamethylpentasiloxane-1-ol (5) in 2-propanol in the presence of alkali metal 2-propanolates and in THF containing 2 vol.-% of water in the presence of NaOH. The results did not confirm our earlier mechanistic proposition. Silanone is not formed intermediately. The process proceeds according to the kinetic law for a bimolecular process and shows a high negative value of activation entropy. However, the reaction exhibits some features better explained by an elimination-addition than by an SN2 mechanism. The hydroxyl group exerts a specific role making the cleavage of the adjacent siloxane bond much easier. The reaction is also accelerated by the assistance of the alkali metal counter ion and its rate seems to be little dependent on the basicity of the nucleophile. A mechanism combining elements of both the SN2 and the elimination-addition pathways is proposed.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870901
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  • 153
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    Emulsion copolymerization of methyl methacrylate with ethyl acrylate, 1. Effect of the initiator concentration on the polymerization behaviour (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2063-2072 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The emulsion copolymerization of methyl methacrylate with ethyl acrylate, initiated by ammonium persulfate in the presence of both anionic and nonionic emulsifiers, was kinetically investigated at 60°C by the conventional gravimetric method. In the range of low conversions the rate of polymerization was found to be proportional to the 0,5 power of the initiator concentration. Over the range of medium conversions the rate of polymerization is approximately proportional to the 0,35 power of the initiator concentration and the number-average molecular weight is inversely proportional to the 0,4 power of the initiator concentration. The molecular weight increases up to 30% conversion and then it remains constant up to the total monomer consumption. It was found that the mean particle diameter decreases while the number of particles per volume unit, the conductivity of final latices, the coagulate yield and the number of radicals per particle increase with increasing concentration of the initiator.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870903
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  • 154
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    Polymeric prodrugs, 5Part 4: cf. M. Azori, J. Pató, F. Fehérvári, F. Tüdős, Makromol. Chem. 187, 303 (1986).. Dextran-bound antirheumatic agent naproxen (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2073-2080 
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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 dextran-bound antirheumatic agent, Naproxen [(+)-2-(6-methoxy-2-naphtyl)propionic acid] (3) was synthesized by linking the 2-aminoethyl ester of Naproxen to the oxydized dextran via an alkylamine bond. The hydrolytic stabilities of modified dextrans were examined viscometrically. The drug release from polymeric prodrug samples containing 68-172 mg of Naproxen per g product was followed at 37°C by automatic titration at pH 8,4. The first order kinetic constant of hydrolysis, k1, was determined to be 2,46(±0,4) · 10-6 s-1. Acute toxicity tests showed no toxic effect on CFLP mice administered intraperitoneally 300 mg/kg of dextran-bound Naproxen.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870904
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  • 155
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    Polymeric schiff's base chelates and their precursors, 9Part 8: cf.19. Synthesis of covalently and coordinatively bound polymeric chelates and their dioxygen binding in the solid stateDedicated to Prof. Dr. G. Manecke at the occasion of his 70th birthday (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2081-2096 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Covalently bound polymeric cobalt chelates 5 of Co(salen) type were synthesized by copolymerization of 2-hydroxy-5-vinylbenzaldehyde (2) with 4-vinylpyridine and subsequent polymeranalogous reactions. Coordinatively bound polymeric chelates 6 were obtained from Co(salen) and poly(4-vinylpyridine) or its copolymer with styrene. Dioxygen binding studies (volumetric measurements and ESR spectroscopy) revealed that mononuclear superoxo complexes are formed reversibly.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870905
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  • 156
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    Funktionalisierung des perlcopolymerisationsprodukts aus methylacrylat und 1,4-bis(vinyloxy)butan (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 497-512 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ester groups of copolymer beads, prepared from methyl acrylate and 1,4-bis(vinyloxy)-butane, were substituted by aminolysis with hexamethylenediamine or aminoalcohols. The resulting gel carrying amino groups was transferred into an anion exchanger by alkylation with 2-chloroethanol or into a cation exchanger by reaction with succinic anhydride. Hydrazinolysis of the starting copolymer beads resulted in gels with hydrazide groups which subsequently can be derivatized. Gels with hydroxyl groups linked to the matrix by means of spacers were obtained by reaction of the succinylated gels with 2-aminoethanol. Phosphorylation of these hydroxyl groups afforded strongly acidic cation exchangers. The yields of the derivatized products are higher and the preparations are easier than those of the known methods. The 11 gel derivatives synthesized from the starting gel are mechanically stable, resistent to hydrolysis in the pH range between 1 and 14, chemically stable at temperatures up to 130°C and obtainable with a variety of pore sizes. The derivatized, cross-linked polymer beads, applicable in aqueous systems as well as in organic solvents, should find application in chromatography, in solid-phase synthesis and as basic gels in biotechnical processes.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870303
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  • 157
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    Interpenetrating polymer networks based on castor oil, 1Dedicated with a profound sense of admiration and gratitude to the memory of late Prof. Dr. Werner Kern (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 525-531 
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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: Liquid prepolyesters (PPE) were obtained from castor oil and dibasic acids, viz. oxalic, malonic, succinic, glutaric, adipic, suberic and sebacic acids. All these prepolyesters were subsequently copolymerized with acrylamide by radical polymerization initiated with benzoyl peroxide. The resulting prepolyester (PPE)/polyacrylamide (PAm) interpenetrating polymer networks (IPN's) were characterized by elemental analyses, solubility behaviour, IR spectral study, differential scanning calorimetry and thermogravimetry. The transition behaviour was analyses for one IPN by the Ozawa and the Kissinger methods for calculating the various kinetic parameters.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870305
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  • 158
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    Polymer crystallinity and morphology in polysiloxanes. poly(tetramethyl-p-silphenylenesiloxane) and poly(tetramethyl-p-silphenylene/dimethylsiloxane) copolymers (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 455-462 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallinities of polysiloxane homo- and copolymers, measured by DSC and checked by X-ray measurements, are presented. A wide range of crystallization conditions and molecular weight fractions were investigated. The morphological implications of crystallinity changes as a function of molecular weight are discussed in regard to other physical parameters. It is concluded that the dependence of crystallinity and X-ray long period on molecular weight is in accord with a defect interface created via chain entanglements primarily, which are trapped during crystallization. The morphology of the specimens directly reflects their preparative history and molecular weight.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870224
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  • 159
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    New phospholiposaccharides as model glycoconjugates. Synthesis and structural study (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 485-496 
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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: New phospholiposaccharides OT-6-DPPE and OT-2-DPPE were synthesized by linking the α-amino function of the asparagine residue of the glyco-amino acid OT from hen ovotransferrin (that contains only Man and ClcNAc residues) to the primary amino group of the polar head of 1,2-dipalmitoylphosphatidylethanolamine (DPPE) via a suberoyl or a succinoyl bridge. The structural study by X-ray diffraction showed that the phospholiposaccharide OT-6-DPPE exhibits a lamellar structure in concentrated aqueous solution and in the dry state at room temperature; in this lamellar structure, the paraffinic chains are crystallized, hexagonally packed, and tilted as in the Lβ, structure of synthetic phospholipids, while the saccharidic chain adopts an “Y-shaped conformation”, A comparison with the previously synthesized liposaccharide OT-16, formed by the same glyco-amino acid OT but linked to palmitic acid and exhibiting a cubic structure in which the saccharidic chain adopts a slightly deformed “T-shaped conformation”, shows that it is possible to induce a conformational change of the saccharidic chain of hen ovotransferrin by changing the nature of the “hydrophobic moiety” linked to the saccharidic chain.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870302
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  • 160
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    Cationic polymerization of tetrahydrofuran initiated by multifunctional initiators (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 553-559 
    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 multifunctional cationic initiators was synthesized from 1,5,9-cyclododecatriene and from methylbenzenes by the Wohl-Ziegler reaction with N-bromosuccinimid. The initiators were treated with silver perchlorate to prepare star-shaped polytetrahydrofurans with three to six arms.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870308
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  • 161
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    Metal salt catalysed transesterifications of thioesters and their application to polyester syntheses (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 547-552 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The transesterification of S-phenyl thiobenzoate with 1-butanol, catalysed with metal salts, was studied as a model reaction for the polyester synthesis. The metal salts were found to interact with both the alcohol and the thioester. Mn(OCOCH3)2 · 4H2O, the most active catalyst, shows a higher kinetic order as well as a greater temperature dependence than the less active catalyst LiOCOCH3 · 2H2O, whereas the uncatalysed reaction shows the smallest temperature dependence. The application of the catalysts for polyester formation was examined with S,S-diphenyl 1,4-benzenedicarbothioate and triethyleneglycol. The molecular weight of the resulting polyester was found to increase with increasing catalytic activity of the metal salt in the corresponding monofunctional model reaction.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870307
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  • 162
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    Ziegler-Natta polymerization of propene: Cooperative effects of titanium ligands on the steric control of the first addition of monomer (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2145-2151 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A 13C NMR analysis of the methyl and ethyl end-groups in isotactic polypropylene, prepared in the presence of TiCl3- and Til3-based catalysts, was performed and the isotactic regularity of the first propylene unit added to the Ti - alkyl bond was measured. In the presence of the catalyst Til3/Al(13CH2CH3)3 the stereoregulating effects derived from the ethyl and iodine ligands are cooperative, so that the addition of the first monomeric unit is as isotactic as the following propagation steps. A comparison of the chain end-groups of polypropylene obtained in the presence of different catalysts shows that the extent of steric control upon insertion of the first monomer molecule results not only from the presence of alkyl titanium ligands larger than methyl and of titanium halide ligands larger than chlorine, but also from mutual ligand interactions.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870912
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  • 163
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    Influence of termination and transfer on molecular weight distribution of polymers, 2Part 1: cf.12.. Radical-radical termination and monomer chain transfer (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2179-2190 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A non-steady state kinetic treatment is rigorously performed for the free radical polymerization with instantaneous initiation, monomer chain transfer and radical-radical termination. An explicit derivation of the molecular weight distribution function is given, and the expressions for other molecular parameters are provided. By means of the formulae given in this paper, the values of the molecular parameters of the polymer generated can be calculated from the initial conditions of polymerization and monomer conversion or reaction time.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870914
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  • 164
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    Precursors of hydrophilic polymers, 6Part 5: M. Přádný, S. Ševčik, Makromol. Chem. 186, 1657 (1985).. Preferential sorption of water on poly[2-(dimethylamino)ethyl methacrylate] in ethanol/water mixtures (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2191-2198 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The study deals with the kinetic behaviour of atactic and isotactic poly[2-(dimethylamino)-ethyl methacrylate] (PDAEM) and of low-molecular-weight tertiary amines in the quaternization by low-molecular-weight alkyl iodides (Mentschutkin's reaction) in water/ethanol solution at 60°C. Unlike quaternization of PDAEM with methyl iodide and 2-iodoethanol, in the cases of the other alkyl iodides the rate constant of quaternization depends on the initial concentration of the alkyl iodide. The rate constant decreases with increasing concentration of the alkyl iodides. The effect becomes more pronounced in a reaction medium containing 43 wt.-% of water in a mixture with ethanol as compared to azeotropic ethanol. Such behaviour is attributed to the fact that in solution of a water/ethanolic mixture the tertiary amines investigated in this study are preferentially solvated by water.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870915
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  • 165
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    Molar mass dependence of rate constants for random scissions of macromolecules (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2209-2213 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reported initial rate constants of the hydrolyses of oligomers and polymers of cellulose and glycine are shown to depend linearly on the inverse of the initial number of cleavable bonds. The slope of this function may be interpreted by many different assumptions on ultimate, penultimate, etc. effects.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870917
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  • 166
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    13C and 1H NMR study of polymers obtained by polymerization of styrene oxide using diethylzinc/water system as initiator (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2215-2221 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Styrene oxide was polymerized by the initiator ZnEt2/H2O and the structure of the resulting polymers was determined by means of 1H and 13C NMR spectroscopy. Both the crystalline and the amorphous fraction have regular head-to-tail structure indicating that the oxirane ring opens exclusively at the β position. The stereochemistry of the growth of the crystalline, highly isotactic fraction follows first order Markov statistics, while that of the amorphous fraction follows Bernoulli statistics.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870918
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  • 167
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    Nuclear magnetic resonance studies on polymer carbanions, 5Part 4: cf.11.. Polystyryl carbanion with lithium as counter cation and its dimer model compounds (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2199-2208 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Oligostyryllithium was synthesized by the reaction of sec-butyllithium with styrene in diethyl ether at -40°C. Dimer model anions (counter cations: Li and K) of the growing chain ends were synthesized by metallation of 1-methoxy-1,3-diphenylpropane. The structures of the lithium compounds were corroborated by 13C NMR spectroscopy and compared with those of the potassium compounds. As for polystyryllithium and its model compounds, the charge density on the α-carbon increased and that on the phenyl ring of the growing end decreased with increasing molecular weight, while, in polystyrylpotassium and its model compounds, the charge density on the α-carbon increased and the one on the phenyl ring did not change with increasing molecular weight. The temperature change of the 1H NMR spectrum of oligostyryllithium in diethyl ether indicated rotation around the C-1—Cα bond at lower temperatures than in tetrahydrofuran, but the activation energy was the same in both solvents. T1 values of the phenyl carbons in model compound 2b were one to two orders of magnitude shorter than those of the protonated compound.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870916
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  • 168
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    Revival and modification of an ancient osmotic pressure equation (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2235-2239 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An osmotic pressure equation proposed over 50 years ago is found to be consistent with the des Cloizeaux scaling relation for semi-dilute polymer solutions in good solvents. With a physically plausible modification, the equation can also give a satisfactory representation of dilute solutions and of the cross-over to the semi-dilute regime.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870920
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  • 169
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    Empirical molecular weight distribution functions as determined from gel permeation chromatography dataDedicated to Dr. B. Sedláček on the occasion of his 60th birthday (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2223-2234 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two- and three-parameter functions commonly used for the description of the molecular weight distribution of polymers were determined from gel permeation chromatography data for 80 water-soluble samples of polymers derived from glutamic acid. Two methods were applied: the moment method in which two or three different molecular weight averages are used, and a least squares adjustment method using the whole chromatogram. Convergence difficulties observed in the past were overcome, and a fully automated computer procedure was developed. The moment method, although virtually the only one still in use, often gives inexact results: sometimes the type of two-parameter distribution is wrongly assigned, or the description of experimental data cannot be improved by adding yet another parameter. On the other hand, in all cases under study the least squares method gave a function which describes the real distribution within the limits of experimental error. Although the majority of samples could be described by employing one of the common two-parameter functions, the more general three-parameter function, encompassing all two-parameter ones as special cases, has the advantage of wider applicability. It is shown that the standard gel permeation chromatography data often cannot provide reliable values of higher molecular weight moment averages, including M̄z. Hence, it may be inferred that in the description of the experimental molecular weight distribution curves the least squares method should be preferred over the moment method.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870919
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  • 170
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    The crystal and molecular structure of an asymmetric diacetylene monomer, 6-(4-dimethylaminobenzoyloxy)-2,4-hexadiynyl 3,5-dinitrobenzoate (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2241-2249 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal and molecular structure of an asymmetric diacetylene derivative, 6-(4-dimethylaminobenzoyloxy)-2,4-hexadiynyl 3,5-dinitrobenzoate (1), was determined from x-ray diffraction data. The crystals are monoclinic, P21/c with Z = 4 in a unit cell having dimensions, a = 11,116 (1) Å, b = 13,429 (2) Å, c = 14,672 (3) Å, β = 106,84 (6)°. The structure was solved by direct methods and refined by least-squares techniques to an RF of 6,2% for 1 991 independent reflections. The diacetylene backbone chains are almost perfectly parallel to the ac-plane; however, they are displaced from each other in the [010] direction. The solid-state polymerization mechanism is discussed with respect to the geometric disposition of the diacetylene chains, which in this crystal are too far apart to permit polymerization by means of 1,4-addition, consistent with the Baughman mechanistic model.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870921
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  • 171
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    Molmassenabhängigkeit der Geschwindigkeitskonstanten der Adsorption von Polybutylmethacrylat aus Cyclohexan (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2251-2256 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of adsoprtion of poly(butyl methacrylate) on iron powder from cyclohexane as solvent is determined by measuring the polymer concentration during adsorption for different molecular weights. There is an inverse relationship between the rate constant of adsorption k and the molecular weight of polymer. This corroborates theoretical results, which involve the quality of solvent: k ∼ 1/M2a where a is the Kuhn-Mark-Houwink exponent. Thus it is possible to determine the quality of solvent by investigations of adsorption using polymers of various molecular weight. Good coincidence with the a-value received from viscosity data via the Kuhn-Mark-Houwink relationship is achieved in the case of cyclohexane.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870922
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  • 172
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    Molecular characterization of soluble poly(1,4-divinylbenzene) obtained by anionic polymerization of 1,4-divinylbenzene with lithium alkylamide as initiator (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2257-2270 
    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 soluble poly(1,4-divinylbenzene) (PDVB) samples was prepared by anionic polymerization of 1,4-divinylbenzene (DVB) in tetrahydrofuran with a varying amount of diisopropylamine. The dilute solution properties of the PDVB samples were examined with conventional methods including viscosimetry, sedimentation equilibrium, and light scattering measurements. The results suggest a considerable amount of long branches in soluble PDVB though not all of the pendant vinyl groups are consumed to form branches. A tree-like model was proposed for the present system. The data were analysed quantitatively according to this model which yielded a consistent pair of values of the z-average mean-square radius of gyration 〈S2〉z1/2 and the intrinsic viscosity [η].
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870923
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  • 173
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    Characterization of cellulose ethers by 13C NMR, 1. Studies of high molecular weight polymers in solution and in the solid state (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 899-911 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Carbon-13 NMR was used to investigate the structure of a cellulose derivative, ethyl-O-(hydroxyethyl)cellulose (EHEC). Analysis of high molecular weight samples in solution showed that the line widths of the main chain carbon resonances are very sensitive to the concentration of the solution. Above a certain concentration, excessive broadening occurs due to gel formation, which makes a quantitative evaluation of the degree of substitution difficult. If the concentration is decreased below the critical value for gel formation, the use of NMR parameters suitable for quantitative measurements (no NOE and long pulse intervals) leads to excessively long accumulation times. Spectra of solid samples obtained by cross-polarization magic angle spinning (CP-MAS) NMR exhibit better defined resonances of the main-chain carbons than do the spectra of solutions with concentrations above the critical value for gel formation. Variable contact time experiments with a specific sample indicated that a suitable contact time should be 400 μs. The quantitative evaluation of the total degree of substitution by CP-MAS NMR yielded values in agreement with those obtained by GC-analysis.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870419
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  • 174
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    Cyclopolymerization, 12Part 11: T. Kodaira, S. Tsuji, K. Okuyama, Y. Hosoki, Polym. J. 16, 901 (1984). Mechanism of free-radical cyclopolymerization of acryloyl- and methacryloylmethylallylamines (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 933-942 
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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: Cyclopolymerizability of acryloylmethylallylamine (1b) was investigated and compared with that of methacryloylmethylallylamine (1a) which is known to yield a highly cyclized polymer with a small amount of pendant methacryloyl groups. The structural study of poly(1b) revealed that residual unsaturation consists exclusively of allyl groups and the degree of cyclization is very low. ESR measurements on the 1b polymerization system yielded only the acryloyl radical as propagating radical. Thus, 1b is incorporated into the polymer mainly through its acryloyl group and the rate-determining step in the cyclopolymerization process of 1b is intramolecular cyclization. On the other hand, the ESR spectrum of 1a consists of cyclized and uncyclized radicals. In this case intramolecular cyclization does not proceed much faster than intermolecular propagation of the cyclized radical. ESR further revealed that the polymerization of 1a first involves the allyl group and then intramolecular cyclization occurs. The difference in cyclopolymerizabilities between 1a and 1b may be interpreted on the basis of the hypothesis that the lower the polymerizabilities of the monofunctional counterparts of unconjugated dienes, the higher their cyclopolymerizabilities.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870422
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  • 175
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    Complex formation of polyampholyte with proton-accepting polymers through hydrogen bonding (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 967-975 
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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: Polyampholytes, copolymers of methacrylic acid and 2-dimethylaminoethyl methacrylate [C(MA-AM)x] of various composition, were synthesized. Their isoelectric points (pI) are in the range 5 〈 pH 〈 7. Undissociated methacrylic acid residues in the copolymers can interact with ether oxygens of poly(ethylene glycol) (PEG) and ketone groups of poly(N-vinyl-2-pyrrolidone) (PVPo) in the acidic pH region through hydrogen bonding. However, only copolymers having more than about 60 mol-% of methacrylic acid residues form complexes with PVPo and high molecular weight PEG. The composition of the obtained complexes is 1:1 (mole ratio of methacrylic acid residues of the copolymer to repeating units of PVPo and PEG).
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870425
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  • 176
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    Comparison of different polymolecularity correction formulae for the burchard-stockmayer-fixman relationshipDedicated to Professor Teiji Tsuruta on the occasion of his 65th birthday (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 955-966 
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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: Polymolecularity correction of the original and the modified procedure according to Burchard, Stockmayer and Fixman, especially useful for the determination of the unperturbed dimensions of macromolecules, is derived via the general “principle of corresponding averages” and compared with the polymolecularity correction methods published by Sutter et al. and Rosenvasser et al. It is shown that the polymolecularity correction factor to be used with the mass-average molar mass in the Burchard-Stockmayer-Fixman relationship is identical to that derived from the corresponding averages of this relationship. Numerical calculations with series of hypothetical monomolecular and polymolecular (exhibiting Schulz-Zimm distributions of the molar mass) polymer-homologous polymer samples in three different thermodynamically good solvents also demonstrate the superiority of the correction method according to Sutter et al. as compared to the correction method of Rosenvasser et al.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870424
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  • 177
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    The monomer content of polymers from bis(hydroxyethyl) terephthalate (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1005-1008 
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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 monomer content in polymers from bis(hydroxyethyl) terephthalate was previously found by Challa to be up to 63% higher than predicted by the classic equations of Flory. A reexamination shows that the apparent anomaly is caused by the approximative nature of the Flory equations which neglect the molar mass of the leaving molecules. Comparison of the experimental data with the predictions of the rigorous theory lowers the difference between experiment and theory significantly. The remaining differences scatter too much to allow any conclusions about a molar mass dependence of equilibrium or rate constants.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870428
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  • 178
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    Termination processes in free radical polymerization, 5Part 4: cf.7.,Part of a poster presentation by O. F. Olaj, G. Zifferer, and G. Gleixner at “Makromolekulares Kolloquium”, Freiburg, GFR, March 4-6, 1982.,Part of the Doctoral Thesis of G. Zifferer, University of Vienna, 1982. The numerical solution of a kinetic scheme with chain length dependent terminationAffectionately dedicated to Prof. DDr. K. Kratzl, Institute of Organic Chemistry of the University of Vienna, my (O.F.O.) former teacher and present friend, on occasion of his 70th birthday (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 977-994 
    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 assess the general consequences of an eventual chain length dependence of the bimolecular termination rate constant kt in free radical polymerization, an iterative procedure for solving the kinetic scheme was developed for this case. The iteration process is based on the equation for the propagation probability of a radical chain of length x, αx, which constitutes a cyclic definition of the α-values, \documentclass{article}\pagestyle{empty}\begin{document}$$ \alpha _x = \left[{{1} + {\nu _{\rm o} ^{ - 2}} \sum\limits_y {F \left( {x,y} \right)} \prod\limits_{i = 1}^y {\alpha _i }} \right]^{ - 1} = \left[{\rm R} _x \right]/\left[{\rm R} _{x - 1} \right]$$\end{document} with F(x,y) giving the functional dependence of kt = kto F(x, y) on the lengths x and y of the two radicals involved in the termination process. As, in addition, αx links the stationary concentrations of radicals of adjacent length, [Rx-1] and [Rx], solving for the set of αx allows to build up the complete chain length distribution of polymer radicals from which all relevant kinetic quantities may be calculated. The following types of functional dependence have been used in practice \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} F_1 \left( {x,y} \right) = \left[ {2xy/\left( {x + y} \right)} \right]^{ - b} \left( { = {\rm harmonic \ mean}} \right) \\ F_2 \left( {x,y} \right) = \left[ {xy} \right]^{ - b/2} \left( { = {\rm geometic \rm mean}} \right) \\ \end{array}$$\end{document}The case of F2, which is the slightly less realistic one, allows to separate the variables x and y in the equation for αx, thus leading to an immediate comfortable solution. Irrespective of the type of F(x, y) chosen (the differences being quantitative in nature rather than qualitative) it can be shown that nearly all the familiar relationships known from “classical” polymerization kinetics with chain length independent termination (b = 0) break down. The new relationships, however, can be cast into comparatively simple power laws. The general consequences of the concept of chain length dependent termination are discussed in some detail.
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  • 179
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    Unified study of the mechanical and optical properties of polyoxymethylene applying the composite model for the temperature range from -60 to 120°C (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1017-1022 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A unified study of the optical and mechanical properties of polyoxymethylene (POM) is attempted in the framework of the composite model for a wide range of temperature (-60 to 120°C) which covers a region well below and above the γ-relaxation temperature. It was found that the existing two phase models for semicrystalline polymers are not adequate for interpreting the mechanical properties of POM over a wide temperature and drawing ratio range. The composite model takes into consideration the effects due to the change in crystallinity and orientation on drawing. The elastic moduli of the composite units are also calculated in terms of those of its constituents. The orientational changes on drawing were directly computed from the birefringence data. It was observed that the general agreement of the calculated and experimental values of the elastic moduli over the entire temperature and drawing ratio range is quite satisfactory.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870430
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  • 180
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    Composite model calculation of the mechanical properties of polypropylene (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1023-1034 
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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 theoretical interpretation of the anisotropic elastic properties of polypropylene is given. It was found that none of the existing models provide a unified description of the mechanical and optical properties of ultradrawn polypropylene. The composite model proposed by the authors, which takes into account the change in orientation and crystallinity on drawing, was applied to investigate the elastic moduli data of polypropylene for a wide range of temperature (-40 to 110°C) and over the entire drawing ratio range. The relationship between θ and θ′, the angles made by the C-axis of the composite unit with drawing direction, was found to be adequately described by the relation tan θ = φ(n) tan θ′. It was further observed that φ(n) in the above relation obtained from birefringence data predicts the correct orientational changes on drawing for the temperature range -40 to 24°C. This makes the evaluation of mechanical properties possible without introducing any arbitrary parameter. However, it is noticed that a particular analytical form of φ(n) with two parameters is quite successful in interpreting the mechanical properties data over the entire temperature range. The abrupt changes of the parameters at certain temperatures seem to be correlated with the β-relaxation and glass transition temperature.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870431
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  • 181
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    Reusable heterogeneous catalysts of α-amino acid racemization, 1. Immobilization of 4-hydroxy-3-formylbenzenesulfonic acid (5-sulfosalicylaldehyde) on strongly basic anion exchangers (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1065-1076 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Strongly basic anion-exchange resins in OH- form, partially neutralized with 4-hydroxy-3-formylbenzenesulfonic acid (5-sulfosalicylaldehyde) (SSA) could be shown to catalyse the racemization of neutral and basic optically active α-amino acids in the presence of copper (II) ions at moderate temperatures (25-45 °C). Under these conditions (S)-asparagine is racemized without hydrolysis of its amide groups. The heterogeneous racemization of (S)-alanine is accelerated by a factor of 880 as compared to a homogeneous reaction. The efficiency of heterogeneous catalysis depends on (1) the extent of neutralization of anion exchanger with SSA, (2) the type of the resin used and (3) the quantity of Cu(II) ions in the reaction mixture. The experimental data are in accordance with the fact that heterogeneous racemization of amino acids proceeds via the formation of a reactive copper(II)-Schiff's base complex. The heterogeneous catalysts can be recycled. The anion exchangers can be regenerated and, if necessary, re-used.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870503
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  • 182
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    New polymeric phosphonato-, phosphinato- and carboxybetaïnes, 1. Syntheses and characterization by IR spectroscopy (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1097-1107 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Neutral phosphonato-, phosphinato-, and carboxybetaïne moieties linked to various polymer supports, poly(styrene-co-4-vinylpyridine) and poly(styrene-co-4-dimethylaminomethylstyrene), were synthesized by a two step sequence. These products were characterized by means of FTIR analysis. Complexing properties towards transition metal salts are outlined.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870506
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  • 183
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    Reusable heterogeneous catalysts of α-amino acid racemization, 2Part 1: cf.1.. Factors affecting the activity of heterogeneous catalysts based on strongly basic anion exchangers in OH- form and 4-hydroxy-3-formylbenzenesulfonic acid (5-sulfosalicylaldehyde) (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1077-1086 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of (S)-Ala racemization on heterogeneous catalysts based on eight strongly basic anion exchangers modified with 4-hydroxy-3-formylbenzenesulfonic acid (5-sulfosalicylaldehyde) (SSA) in the presence of Cu(II) ions at 25 °C was studied. The “internal capacity” value f = mp/(V0  -  Vp) was introduced to characterize the polymers, (mp : number of quaternary ammonium groups of the polymer sample, V0 : total volume of the swollen polymer, Vp : volume of the inert polymeric matrix). The correlation of the observed first-order rate constants of (S)-Ala racemization with the f values of the anion exchangers was established. According to this correlation the selected anion exchangers could be divided into two types with respect to the chemical nature of the groups attached to the quaternary nitrogen atom. The chemical nature, physical structure and the degree of cross-linking of the polymeric matrix do not affect the correlation. Anion exchangers of the first type have at least one ß-hydroxyalkyl substituent at the \documentclass{article}\pagestyle{empty}\begin{document}$ - \mathop N\limits^ \oplus {\textstyle{/ \over \backslash }} $\end{document} Anion exchangers of the second type have \documentclass{article}\pagestyle{empty}\begin{document}$\mathop {\rm N}\limits^ \oplus $\end{document}(CH3)3 cationic groups. Catalysts prepared with the first type anion exchangers have greater activity as compared with catalysts based on the second type anion exchangers with the same f values. The increase in activity of heterogeneous catalysts can be partially attributed to the 10 to 68 fold increase in OH- concentration in the internal phase of the catalysts as compared to the model homogeneous system, which contains the same amounts of the components as the heterogeneous one. Moreover, an additional acceleration is observed in the heterogeneous racemization as compared to the homogeneous one, ca. 5 fold for the second type anion exchangers and ca. 14 fold for the first type anion exchangers.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870504
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  • 184
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    DNA protonation at low ionic strength of solution (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1053-1063 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: UV differential spectroscopy and thermal denaturation were applied to investigate the protonation of native (6 °C) and denatured (70 °C) DNA at 10-3M of Na+ in the range of pH 7,0 to 3,85. A decrease in the pH was found to deteriorate the thermal stability of DNA and to narrow the range of the helix-coil transition due to preferential destabilization of G + C pairs. The pH dependence of the degree of helicity for native DNA is non-monotonic and agrees with the protonation model proposed by Courtois et al. The proton binding to the bases is anticooperative for native DNA and noncooperative for denatured DNA. The ionization of the bases is characterized by pK′ = 4,7 for helical and by pK′ = 5,2 for coil DNA.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870502
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  • 185
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    Interaction of 14CO with Ziegler-type heterogeneous catalysts and effect of interaction products on the determination of the amount of active centers (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1041-1051 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The interaction of 14CO with Ziegler-type heterogeneous catalysts (titanium-magnesium catalysts, titanium trichloride) in the absence of an olefin was studied. This reaction was found to produce radioactive products soluble in hexane. Formation of such products takes place in the presence of both titanium chloride and AlR3, and is attributed to the insertion of 14CO into the Ti-R bonds. For titanium-magnesium catalysts the number of labels in hexane may exceed the number of titanium atoms in the catalysts, which indicates that the Ti-R bond may be regenerated by AlR3. In the starting phase labelled products are formed at maximum rate, which is an evidence that a rapid insertion of 14CO (some minutes) into Ti-R bonds takes place. The effect of side labelled products on polypropylene radioactivity is examined and the necessity to purify the polymers from radioactive impurities is shown. The influence of the side process of the interaction of 14CO with the catalytic system on the determination of the amount of active centers is discussed.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870501
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  • 186
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    Polymerizable tautomers, 1. Tautomerism and polymerization of ethyl 3-oxo-4-pentenoate (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1087-1095 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvent effects on the tautomerism and polymerization of ethyl 3-oxo-pentenoate (1) were studied. Regression analysis of the tautomeric constant reveals that the equilibria depend on the polarity and hydrogen-bond donor acidity of the solvents. The polymerization was investigated in benzene and acetonitrile. In both solvents, the kinetic results do not meet the conventional model of radical polymerization.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021870505
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  • 187
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    Reversible copolymerization at equilibrium (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1109-1114 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relationships for copolymer composition and microstructure in reversible copolymerization at equilibrium are derived. They allow to predict the comonomer equilibrium concentrations and the structure of the copolymer at equilibrium if the initial state and equilibrium constants are known and provided that [I] ≪ [M1]0 + [M2]0 - [M1]e - [M2]e.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870507
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  • 188
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    Liquid crystalline polyesters with 1,4-cyclohexylene units (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1145-1150 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new series of liquid crystalline polyesters (5a - f) containing 1,4-cyclohexylene dibenzoate moieties as mesogenic units in the main chain was prepared and characterized. The rigid segments in the polymers are connected by α,ω-alkanedioyl units containing 4-8 or 10 methylene groups.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870511
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  • 189
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    Polymerization of propene in the presence of MgCl2-supported Ziegler-Natta catalysts, 2Part 1: cf.1.. Effects of the co-catalyst composition (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1115-1124 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: As a part of a study on the polymerization of propene in the presence of MgCl2-supported catalysts, new results were obtained when polymerizing at variable ethyl benzoate (EB)/alkylaluminium and alkylaluminium/Ti mole ratios. The pre-treatment of MgCl2 with the Lewis base is essential to achieve high stereoregularities without an unacceptable decrease of polymerization rate, apparently because it prevents the formation of nonstereospecific active sites of low Lewis acidity, which require high EB/alkylaluminium mole ratios in the co-catalyst in order to be poisoned. The data may be explained in the framework of a model of catalytic sites preliminarily presented in Part 1 of this series.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870508
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  • 190
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    Poly(ethylene glycol)s containing enzymatically degradable bondsPart 10 in the series “Polymers containing enzymatically degradable bonds”. Part 9: cf.10.Dedicated to Dr. B. Sedláček on the occasion of his 60th birthday (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 1131-1144 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The possibility to use poly(ethylene glycol) (PEG) as a synthetic, water-soluble polymeric carrier of biologically active compounds was investigated. The relationship between structure of oligopeptide (amino acid)-PEG conjugates and their hydrolysis catalyzed by chymotrypsin was studied. Two types of derivatives were synthesized: Derivatives of PEG 2000, containing an oligopeptide sequence terminating in p-nitroaniline (drug model) and higher molecular weight derivatives of PEG 2000 containing in the main chain enzymatically and hydrolytically degradable bonds. The rates of chymotrypsin catalyzed release of p-nitroaniline at pH 8,0 and 25°C were determined over a range of substrate concentrations to derive values for kcat and KM. The influence of the length and detailed structure of the oligopeptide sequence on the rate of hydrolysis was demonstrated. Comparison with copolymers of N-(2-hydroxypropyl)methacrylamide and poly(maleic anhydride-co-vinylpyrrolidone) showed that the sterical hindrance of the formation of the enzyme-substrate complex is much less pronounced in the PEG-oligopeptide conjugates. The latter conclusion is also valid in the case of cleavage of PEG derivatives which contain enzymatically degradable bonds in the main chain. The incorporation of a single amino acid residue (phenylalanine) into the main PEG chain is sufficient to make the polymer susceptible to chymotrypsin catalyzed hydrolysis.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870510
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  • 191
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    Interactions of human hemoglobin with high-molecular-weight dextran sulfate and diethylaminoethyl dextran (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2567-2578 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The binding of hemoglobin with high molecular weight dextran sulfate and diethylaminoethyl (DEAE) dextran was studied by turbidimetry, viscosimetry, ultrafiltration and oxygen affinity measurements. The results indicate that a complex is formed between hemoglobin and the charged dextrans through salt bridges. This complexation can lead to precipitation if the ionization degree of hemoglobin is high enough to develop an extensive neutralization of the charges of polyionic dextrans. At the pH value near to the isoelectric point, complexation still occurs, probably through salt bridges between the polyelectrolytes and the ionized sites of opposite charge on the hemoglobin molecule, but the complexes remain soluble in solution. Binding appears to be stronger for the hemoglobin-dextran sulfate compounds than for the hemoglobin-DEAE dextran compounds. The oxygen affinity of hemoglobin is greatly decreased in the presence of dextran sulfate, indicating a stabilization of the deoxyhemoglobin with respect to the oxyhemoglobin.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021871106
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  • 192
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    High molecular weight chitosan 6-O-sulfate. Synthesis, ESR and NMR characterization (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2609-2620 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Selective sulfation of the primary hydroxyl group of chitosan was performed by means of the pyridine-SO3 complex after the positions 2 and 3 of the aminoglucopyranosidic ring were protected by coordination with copper ions. The requirements for complexing copper ions were investigated as a function of the pH and Cu(II)/chitosan mole ratio of the starting solution. Cu(II)-chitosan complexes were characterized by ESR and 13C NMR CP-MAS investigations; two different paramagnetic Cu(II) species were observed, whose relative quantity changes by changing the pH of the starting solution. The g tensor values (species I: g1‖ = 2,28, g1‖ = 2,06, A2‖ = 160 G; species II; g2‖ = 2,24, g2‖ = 2,06, A2‖ = 160 G) are consistent with a CuN2O2 chromophore. The sulfation reaction was studied in the range of 25 to 75°C using 2 : 1 to 6 : 1 pyridine-SO3/Cu(II)-chitosan mole ratios. Under optimized reaction conditions, a selective 6-O sulfation was obtained in more than 90% yield.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021871110
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  • 193
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    Influence of termination and transfer on molecular weight distribution of polymers, 5Part 4: cf.2.. Chain transfer to monomer and impurity termination (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2629-2640 
    Details
    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 simultaneous effect of impurity termination and chain transfer to monomer on the molecular size distribution for the anionic polymerization with instantaneous initiation was studied theoretically in detail. The rigorous expressions for the molecular size distribution function and other molecular parameters were derived from a set of kinetic differential equations by means of the non-steady state method. In accordance with these expressions, several examples of numerical calculation are given and a comparison is made between the polymerization system with chain transfer to monomer and that without monomer transfer.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021871112
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  • 194
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    The characteristic ratio of poly(methacrylic acid) in organic solvents (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2621-2628 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Parameters of the Mark-Houwink equation for poly(methacrylic acid) (PMAA) in methanol at 25°C, [η] = 0,0224 · M0,679, were determined and found to differ markedly from those reported earlier for 26°C. The value of the exponent along with the high value of the second virial coefficient confirms that near to 25°C methanol is not a theta-solvent for PMAA. By employing extrapolation according to Tanaka, the characteristic ratios C of PMAA in methanol (C = 12,0) and in 2-ethoxyethanol (C = 9,7) were determined from viscosity data at 25°C. The unperturbed dimensions of PMAA depend on the solvent used. They are larger in organic solvents than in water, but the difference is not so high as assumed before. By using the Stockmayer-Fixman extrapolation, the characteristic ratio for PMAA in 2-ethoxyethanol was determined at 70°C, i.e. at a temperature not too far from theta-conditions (Θ = 65°C, C = 8,2). A comparison with the value for 25°C shows that the unperturbed dimensions of PMAA decrease with increasing temperature.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021871111
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  • 195
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    Influence of termination and transfer on molecular weight distribution of polymers, 6Part 5: cf.8.. Chain transfer to monomer and spontaneous termination (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2641-2648 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the previous parts of this series, a mathematical procedure was developed for the derivation of molecular size distribution functions of polymers generated in several ionic polymerizations. This paper follows this mathematical procedure to treat theoretically the kinetics of cationic and anionic polymerizations with instantaneous initiation, chain transfer to monomer, and spontaneous termination. The expressions of molecular size distribution functions and other molecular parameters are derived rigorously. Moreover, the simultaneous influence of chain transfer to monomer and spontaneous termination on molecular size distribution is illustrated by means of several numerical examples.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021871113
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  • 196
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    Free-radical polymerization of methyl methacrylate at very high conversions, 2Part 1: cf.1.. Study of the kinetics of initiation by benzoyl peroxideDedicated to Dr. F. Kollinsky on the occasion of his 60th birthday (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2663-2673 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The initiation kinetics of the free-radical polymerization of methyl methacrylate at very high monomer conversions was investigated at 80, 100, and 120°C. Using a HPLC (high performance liquid chromatography) analytical technique with UV detection, the consumption of both monomer and initiator as well as the formation of reaction products of the latter could be followed. It was found that (besides very small amounts of biphenyl and benzoic acid) phenyl benzoate is the main decomposition product. The experimental results were analyzed quantitatively with the help of a reaction scheme which takes into account the most important pathways of that complex chemical reaction system. Thus, it was found that, due to the very strong cage effect in the present polymerization system, the experimentally accessible (apparent) first order rate constant of initiator decomposition is substantially lower than that for the primary cleavage of a benzoyl peroxide molecule. Efficiencies of chain initiation were calculated to be in the range of 0,1 to 0,2 in the (nearly) glassy polymer matrix.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021871116
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  • 197
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    Group transfer polymerization of methacrylonitrile (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2691-2696 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The group transfer polymerization of methacrylonitrile in acetonitrile, initiated by 2-(trimethylsilyl)isobutyronitrile in presence of tetraethylammonium cyanide or tetrabutylammonium fluoride as coinitiator, is accompanied by an anionic polymerization initiated by the coinitiator alone so that polymers with bimodal molecular weight distributions are formed. In contrast, with tris(dimethylamino)sulfonium difluorotrimethylsilicate as coinitiator a pure GTP is observed leading to polymers with unimodal molecular weight distribution. In all systems, severe side reactions reduce conversions and molecular weights.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021871119
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  • 198
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    Effect of the number of crystallizable blocks on the lamellar crystalline structure of block copolymers from poly(4-tert-butylstyrene) and poly(ethylene oxide)Dedicated to Prof. Dr. R. C. Schulz in honour of his 65th birthday (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2685-2690 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Linear block copolymers tBSEO with an amorphous block of poly(4-tert-butylstyrene) (PtBS) and a crystallizable block of poly(ethylene oxide) (PEO) as well as branched block copolymers tBS(EO)2 with two PEO chains linked at the same end of a PtBS block exhibit a lamellar liquid-crystalline structure in the dry state as well as in the presence of a preferential solvent of the PtBS block. In this structure the crystallized chains are folded in two superposed layers. To investigate the effect of the number of the PEO blocks, a linear and a branched copolymer with identical relative molecular masses and copositions were studied by X-ray diffraction and differential scanning calorimetry. It was shown that the melting temperature, the degree of crystallinity, and the number of folds of the PEO chains are higher for the linear copolymer than for the branched one.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1986.021871118
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  • 199
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    The effect of units derived from diethylene glycol on crystallization kinetics of poly(ethylene terephthalate) (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2697-2709 
    Details
    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 units derived from diethylene glycol (DEG) on the crystallization behaviour and linear growth rate of spherulites of poly(ethylene terephthalate) (PETP) free of metal catalyst residues, is studied by means of differential scanning calorimetry (DSC), small-angle light scattering (SALS), polarized light microscopy (PLM), and transmission electron microscopy (TEM). The results show that the crystallization behaviour does not depend only on the temperature of crystallization, but also on a large scale on the content of DEG. In hot crystallization, the rate of PETP crystallization decreases with increasing DEG content; in cold crystallization, this effect is not so prominent. The higher the DEG content, the smaller is the number of nuclei and therefore the linear growth rate of PETP and, at the same time, the size of the spherulites becomes greater.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021871120
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  • 200
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    Miscibility of linear and branched polyethylene in the liquid state (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2725-2730 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: HDPE/LDPE blends and the pure components were crosslinked either by irradiation or by di-tert-butyl peroxide in the liquid state. The degree of crosslinkage was characterized by the reciprocal degree of swelling Q-1 (xylene, 2 h, 140°C). Above a critical degree of crosslinkage corresponding to Q-1 = 0,2 the DSC curves of HDPE/LDPE blends show only one single crystallization peak on cooling from the melt and only one single melting peak on subsequent heating. This is an unequivocal proof for the single phase structure of HDPE/LDPE blends in the liquid state. Crosslinking with Q-1 ≥ 0,2 prohibits fractional crystallization and forces the unbranched CH2 sequences of both components between the crosslinks into one crystal lattice.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021871122
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