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  • American Association for the Advancement of Science (AAAS)
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  • 201
    Electronic Resource
    Electronic Resource
    Investigation of the electrical conductivity of the iodine-polyphenylacetylene charge-transfer complex (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 165-176 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The electrical conductivity of the charge transfer complex between iodine and polyphenylacetylene (PPA) has been studied. The room temperature d-c conductivity (σ) increased by seven orders of magnitude with iodine addition, reaching a maximum of 10-5 Ω-1 · cm-1 for a 1:1 ratio of iodine to repeating unit, and its concentration dependence could be described by: σ = σ0 exp [γc(1-c) - γ/4], where c is the mole fraction of iodine. Both crystalline and amorphous cis-PPA followed this form, the crystalline polymer having a lower conductivity at low iodine levels, but attaining the same maximum value. The trans-polymer iodinated much less readily than cis-PPA. Molecular weight variations did not influence iodine uptake or conductivity in the range studied. It was possible to remove virtually all iodine from the charge-transfer complex in dynamic vacuum, and an iodine diffusion coefficient of D ≈ 10-11 cm2.s-1 was determined from the rate of weight loss. Passage of current resulted in the evolution of iodine and iodine compounds at the anode. The experiment is consistent with a predominantly ionic conduction mechanism, in which the strong concentration dependence of σ is associated with a concentration-dependent activation energy for ionic charge-carrier formation.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820118
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  • 202
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    Polymerization of 1,3-cycloheptadiene and the structure of poly(1,3-cycloheptadiene)s obtained by ionic initiators (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 215-217 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820123
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  • 203
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    The colour reaction between poly(vinyl alcohol) and iodine-iodide in the presence of orthotelluric acid (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 225-229 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820125
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  • 204
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    Studies on carboxymethylcellulose: Potentiometric titrations, 3 (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 243-245 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820128
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  • 205
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    A new structure for polystyrene-polybutadiene block copolymers: A smectic E type structure (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 265-268 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820132
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  • 206
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    A new convenient method for the synthesis of poly(styrenesulfonic acid) (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 279-281 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820135
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  • 207
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    Controlled release of fluoride ions from methacryloyl fluoride  -  methyl methacrylate copolymers, 1. Synthesis of methacryloyl fluoride  -  methacrylate copolymers (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 273-277 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820134
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  • 208
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    Syntheses of polymeric cobalt dinitrogen complexes and reduction of the coordinated nitrogen (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 283-291 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymeric cobalt dinitrogen complexes were synthesized by two different methods: by the ligand substitution reaction of polymers 5a - c and 6a - c, containing 4-diphenylphosphinophenylethylene units (3) or 4-diphenylphosphinomethylphenylethylene units (4), respectively, with hydridodinitrogentris(triphenylphosphine)cobalt(I) (CoH(N2)(PPh3)3), or by the direct reaction of tris(acetylacetonato)cobalt(III) with triphenylphosphine, the polymers 5a - c or 6a - c, and triisobutylaluminium under nitrogen. The intensity of the vN2 band in the IR spectrum of the polymeric dinitrogen complex was found to be about four times as that of CoH(N2)(PPh3)3. Ammonia was formed after hydrolysis of the complex, which was prepared by mixing a tetrahydrofuran solution of naphthaline, lithium, and titanium tetrachloride with the polymeric dinitrogen complex. The yields of ammonia in the case of the polymeric complexes were high in comparison with that obtained with CoH(N2)(PPh3)3. The highest yields of ammonia were obtained when a mole ratio [P̄]/[Co] 〈 1 ([P̄] is the concentration of phosphino groups in the polymer and [Co] is that of Co in CoH(N2)(PPh3)3), a temperature of -20°C, and a reaction time of 1 h were applied.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820201
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  • 209
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    Synthesis and conformational study of poly(L-valyl-L-valyl-∊-N-benzyloxycarbonyl-L-lysine) in the solid state and in solution (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 549-557 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: High molecular weight poly(L-valyl-L-valyl-∊-N-benzyloxycarbonyl-L-lysine) (PVVZL) (7) was obtained by condensation in dimethyl sulfoxide of the L-valyl-L-valyl-∊-N-benzyloxycarbonyl-L-lysine p-nitrophenyl ester, synthesized by the DCCStandard abbreviations for amino acid derivatives and peptides are used according to the I.U.P.A.C.-I.U.B. Commission on Biochemical Nomenclature, Biochemistry 11, 1726 (1972). The abbreviations used are: Boc = tert-butyloxycarbonyl; Z = benzyloxycarbonyl; OBzl = benzyl ester; H-Val-OH = valine; H-Lys-OH = lysine; HONp = para-nitrophenol; DDC = dicyclohexylcarbodiimide; DMSO = dimethyl sulfoxide; TFA = trifluoroacetic acid; TFE = 2,2,2-trifluoroethanol; CD = circular dichroism; IR = infrared spectra. method. The conformation of 7 was studied in the solid state and in solution of 2,2,2-trifluoroethanol, acetonitrile-trifluoroethanol and dioxane-trifluoroethanol mixtures by X-ray diffraction method, CD and IR spectroscopy. The results obtained in the solid state suggest the presence of β-structure, whereas in trifluoroethanol solution, at least, a mixture of random coil and β conformation, probably occurs. The aging of the solution seems to give rise to a higher content of β-structure. The addition of acetonitrile and dioxane favours the formation of an increasing amount of β-structure. Therefore, the conformational behaviour of 7 is similar to that of other sequential polypeptides containing valyl residues, which seem to promote the β-structure.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820221
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  • 210
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    Small angle neutron scattering of molten n-alkane/polyethylene mixturesPresented at the Hamburg Macromolecular Symposium, September 16 - 18, 1980. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 583-587 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820225
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  • 211
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    Spinodale Entmischung von Defekten in Nadelkristallen aus isotaktischem PolypropylenVorgetragen auf dem Hamburger Makromolekularen Symposium 16. - 18. September 1980. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 613-619 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820229
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  • 212
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    Herstellen von Hochmodulfäden aus PolyethylenVorgetragen auf dem Hamburger Makromolekularen Symposium 16. - 18. September 1980. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 637-642 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820232
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  • 213
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    The configurational characteristics of conventional poly(methyl methacrylate) in acetonitrile (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 445-449 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The θ-temperature and viscosity constant K0 of radically initiated poly(methyl methacrylate) in acetonitrile were determined from the intrinsic viscosity data (θ = 28°C, K0 = 4,3 · 102 g-3/2 · mol1/2.cm3). The unperturbed coil dimensions are lower in acetonitrile than in other θ-solvents at comparable temperature and indicate a more compact conformation of poly(methyl methacrylate) molecules. The discrepancies in the reported data of the θ and K0 values are elucidated.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820215
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  • 214
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    Messungen zum Aggregationsverhalten perfluorierter AlkansäurenHerrn Prof. Dr. M. Seefelder/BASF zum 60. Geburtstag (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 451-481 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: With the use of various techniques an attempt was made to characterize the aggregates that exist in micellar surfactant solutions of salts of the perfluornonanoic acid. The cmc values of the investigated systems were determined by conductivity and surface tension measurements. Conclusions about the shape of the micellar aggregates were drawn from rheologic and electric birefringence measurements. For the lithium, the ammonium and the tetramethylammonium surfactants the existence of normal micelles with spherical shape and with all surfactant ions lying at the micellar surface was found. The perfluornonanoate surfactants with the ammonium counterions that are partially substituted by alkyl groups showed in all investigations a behaviour that was different from the normal case. It was postulated that these solutions contain emulsion-droplet-like giant micelles with the surfactant ions and counterions solubilized as ion pairs in the interior of the micelles. Some of these giant micelles do not have spherical shape; these solutions showed electric birefringence. In most cases the giant micelles disappeared at higher temperatures. Only normal small micelles with spherical symmetry could then be detected and the measured values were again in the range for values of normal C8-perfluordetergents. On the basis of the investigated systems reasons and models for the formation of giant micelles are discussed.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820216
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  • 215
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    Application of electrostatic persistence length to polyelectrolyte solutions (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 559-568 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of added simple salt and polyion charge on the chain flexibility of an alternating copolymer of isobutyl vinyl ether and maleic acid are analyzed. The persistence length of this polymer in aqueous NaCl solution is calculated from sedimentation and viscosity data on the basis of a worm-like chain model. It is found that this polymer is in the state of a highly expanded conformation at low ionic strength, exhibiting a semi-rigid macromolecular behaviour and that it behaves like a rather coiled polymer with small persistence length at high salt concentration. The electrostatic persistence length calculated from the theory of Fixman et al. shows a \documentclass{article}\pagestyle{empty}\begin{document}$ 1/\sqrt {C_{\rm s} } $\end{document}-dependence on added salt concentration Cs.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820222
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  • 216
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    Effect of adjacent functional groups on the electron-donor-acceptor complex formation of diethyl 2,2-bis(dinitrobenzyl)malonates and 2,2-bis(4-dimethylaminobenzyl)malonate (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 739-748 
    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 study the effect of adjacent functional groups on electron-donor acceptor (EDA) complex formation, the following donor or acceptor compounds were synthesized: diethyl 2-(2,4-dinitrobenzyl)malonate (13), diethyl 2,2-bis(2,4-dinitrobenzyl)malonate (14), diethyl 2-(3,5-dinitrobenzyl)malonate (5), diethyl 2,2-bis(3,5-dinitrobenzyl)malonate (6), diethyl 2-(4-dimethylaminobenzyl)malonate (10), diethyl 2,2-bis(4-dimethylaminobenzyl)malonate (11). The acceptor compounds 5, 6, 13, and 14 were complexed with N,N-dimethyl-4-dimethylaminoaniline (1) as donor, and the donor compounds 10 and 11, with 1,3,5-trinitrobenzene (2) as acceptor. The wave length of the absorption maximum (λmax), the association constant (KCT), the enthalpy (δH), and entropy (δS) of these EDA complexes were determined. It was found that λmax of complexes 6-1 and 11-2 show a bathochromic shift compared with complexes 5-1 and 10-2, and the values of KCT, -δH, and -δS are higher. The value of λmax for complex 14-1 is not different from that of complex 13-1, and the values of KCT, -δH, and -δS are lower. It was concluded that the stability of the EDA complexes of the 2,2-dibenzylmalonate derivatives 6, 11, and 14, is influenced by π-electron interaction between the adjacent two benzene rings.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820304
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  • 217
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    Préparation d'adsorbants chromatographiques plurifonctionnels et asymétriques. Application à la purification de la céphalosporine C (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 763-771 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Some asymmetric and polyfunctional stationary phases were prepared by attachment of the ε-amino group of L-lysine copper complex to crosslinked polystyrene or agarose, substituted or not by hydrophilic spacer arms. After copper elimination, the sorbents exhibit three functions, one of a carboxylic acid and one of an α-primary amine, and moreover one of a secondary amine located at a variable distance far from the asymmetric carbon, but near the backbone of polymer. These sorbents were tested in the chromatographic extraction of cephalosporin C (1) from an aqueous mixture containing several α-amino acids. They exhibit an affinity higher for the antibiotic than for the amino acids and even for the dicarboxylic amino acids.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820307
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  • 218
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    Synthesis and electrical properties of monomeric and polymeric iron-phthalocyanines (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 811-816 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A set of experimental conditions are described for the synthesis of monomeric and polymeric iron-phthalocyanines and compared with those reported in the literature. The dielectric constant and resistivity of characterised samples are studied as a function of temperature. The data indicate possible transitions at 90 and 180°C for monomeric iron-phthalocyanine whereas polymeric iron-phthalocyanine shows no breaks.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820311
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  • 219
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    Graft copolymerization of methyl methacrylate on chlorinated natural rubber, 1. Initiation by various organometallic complexes (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 843-851 
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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: Metallic compounds able to abstract chlorine atoms are investigated for initiating the graft copolymerization of methyl methacrylate on chlorinated natural rubber. An improved method for the separation of the side homopolymer from the graft copolymer is described. The cumulative results demonstrate the greater graft efficiency of the new initiating systems than of the usual free radical initiators.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820315
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  • 220
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    Katalysatoren beim thermischen Abbau von Polymeren, 1. Über den katalytischen Abbau von Polypivalolacton (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 867-871 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ability of different metal oxides and acetates to catalyze the thermal degradation of poly(pivalolactone) into cyclic oligomers has been investigated. Magnesium oxide was found to be the most active catalyst which converts poly(pivalolactone) completely into oligomers within less than two hours at 547 K. The influence of temperature and catalyst concentration and the distribution of cyclic oligomers is discussed.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820318
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    Overall and individual effects in systems including organolithium compounds (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 911-915 
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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: Experimental and quantum chemical data are used for the problem of the relative rǒle of individual factors considering the overall effects which are characteristic of certain Licontaining systems. Recourse is made to the following processes: polymerization of isoprene in the presence of subcatalytic amounts of electron donors; polymerization of acrylonitrile by RLi and ROLi initiators; polymerization of dienes by butyllithium (n-BuLi) and tert-butyllithium (tert-BuLi).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820321
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  • 222
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    Adiabatic polymerization of ε-caprolactam in presence of lithium chloride, 1. Thermodynamic and Kinetic aspects (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 929-939 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The activated anionic polymerization of ε-caprolactam in presence of LiCl (up to 10 wt.-%) is studied under quasi-adiabatic conditions. The temperature increase of the system, after proper corrections for the heat exchange with the surroundings, allows to evaluate the enthalpies of polymerization δHp and to correlate their variations with the specific interactions of LiCl with monomer and polymer. The sharp decrease of -δHp as function of LiCl content is attributed to the stabilizing effect of the ion-dipole interactions, which is higher for the monomer-salt pair than for the polymer-salt mixture. The initial rates of polymerization are enhanced by a few percents of added LiCl, with a maximum at about 3 wt.-%. The relative influence of various physical factors on the polymerization kinetics and thermodynamics is discussed.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820324
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  • 223
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    Polymerization of tetrahydrofuran by bifunctional cationic initiators: Terephthaloyl perchlorate (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 731-737 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics and mechanism of the polymerization of tetrahydrofuran with terephthaloyl perchlorate in methylene chloride or cyclohexane were analyzed. This polymerization produces dicationically active polymers and takes place without induction period. Propagation in both solvents proceeds as a reaction being first order in monomer, and it changes with the polarity of the solvent because ionic and covalent species take part with different growing rates. The macroester mole fractions in cyclohexane and methylene chloride are 0,99 and 0,86, respectively.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820303
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  • 224
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    Recherche de télomères à activité pharmacologique potentielle, 2Partie 1: cf.25.. Télomères de l'acide acrylique et greffage de composés hydroxylés (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 773-784 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several telomers of acrylic acid with carbone tetrachloride were prepared. Their average degree of polymerization, which was between 10 and 50, was determined by several analytical methods (elemental analysis, viscosimetry, and GPC). From the kinetic equations of telomerization a relation between DPn of these telomers and the experimental conditions is established. Fixation of hydroxylic compounds through direct esterification was studied and it was found that the prepared telomers can be used as hydrosoluble carriers for drugs containing primary alcohol or phenol functions.
    Additional Material: 10 Tab.
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    Polymers containing enzymatically degradable bonds, 1. Chymotrypsin catalyzed hydrolysis of p-nitroanilides of phenylalanine and tyrosine attached to side-chains of copolymers of N-(2-hydroxypropyl)methacrylamidePresented at the 25th IUPAC Symposium on Macromolecules, Mainz, FRG, September 1979. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 799-809 
    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 copolymers of N-(2-hydroxypropyl)methacrylamide were prepared, which contained side chains of the general formula -Gly-X-Y-NAp, where Gly ¨ glycine; X ¨ glycine, alanine, β-alanine, valine, leucine, isoleucine, phenylalanine; Y ¨ phenylalanine or tyrosine; NAp ¨ p-nitroanilide, the latter modelling biologically active compounds. The rates of chymotrypsin-catalyzed hydrolysis of p-nitroanilide groups at pH = 8,0 and 25°C were determined over a range of substrate concentrations to derive values for kcat and KM. The results allowed us to determine the influence of the structure of side chains on the rate of cleavage of Y-NAp. The increase in the susceptibility to chymotrypsin attack with an increasing spacing of the Y-NAp residue from the backbone of the polymer chains is demonstrated by comparing the kinetic data of copolymers containing -Gly-Gly-Phe-Phe-NAp, -Gly-Gly-Phe-NAp and -Gly-Phe-NAp side chains. Results obtained with α-chymotrypsin were compared with the cleavage of the above polymer substrates with chymotrypsin covalently bound to a copolymer of N-(2-hydroxypropyl)methacrylamide.
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    Synthesis and properties of aromatic polypyrazoles from bis(β-substituted vinyl ketones) and aromatic dihydrazines (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 837-842 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polycyclocondensations of aromatic dihydrazines 2a and 2b with 1,6-diethoxy-1,5-hexadiene-3,4-dione (1a) in m-cresol and those with bis(3-chloroacryloyl)benzenes 1b and 1c in 1-methyl-2-pyrrolidone (NMP) lead to aromatic polypyrazoles 3a - f having inherent viscosities up to 0,35 dl.g-1. The polymers are soluble in polar aprotic solvents like NMP and some acidic media including m-cresol. Thermogravimetry shows a loss of 10 wt.-% at ≈ 500°C both in air and nitrogen.
    Additional Material: 1 Ill.
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    Synthesis of polyamides containing 4,4′-azodibenzamido unitsPaper presented at the International symposium on“New Frontiers in Polymer Science and Polymer Applications”, held at Madras (1980). (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 853-859 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Four coloured polyamides containing azo-p-phenylene units were synthesised from 4,4′-azodibenzoic acid and four aromatic diamines employing both interfacial and solution polymerization procedures. The polymers were characterized by their UV and IR spectra, by inherent viscosity measurements and by solubility data. The stability in conc. sulfuric acid and the thermal behaviour are discussed.
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    Caractérisation texturale de résines en milieu réactionnel (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 873-882 
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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: Thermoporometry, a method based on the microcalorimetric analysis of liquid-solid state transformation inside porous substances, gives access to porous volume versus pore size distribution. For the first time, this method is applied to the analysis of flexible products swellable in the reference medium. Conditions for applying transposition thermoporometry to this new class of porous substances are discussed. An example is given, which leads to suggest a model for the swelling process of a macroporous resin. Generalization of this method would induce a major progress in the study of swollen systems and enable better understanding of their structures.
    Additional Material: 5 Ill.
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    Subkatalytische Effekte in Systemen Isopren/Organolithium/Elektronendonator, 3Teil 2: cf1.. System Isopren/Oligoisoprenyllithium/1,2-Dimethoxyethan (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 917-920 
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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: Molecular weights and structural characteristics of the polymers formed in the system isoprene/oligoisoprenyllithium (OILi)/1,2-dimethoxyethane (DME)/hexane (mole ratio DME/OILi = 0,01) for various conversions at -30°C were determined. The results obtained corroborate the former conclusion that the complexation of an electron donor with the monomeric form of the growing chain reduces the reactivity of the latter.
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    Polymethacrylic acid Derivatives, 1. Preparation, Characterization, and Potentiometric study of poly(N-methacryloyl-L-alanine-co-N-phenylmethacrylamide) (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 949-963 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(N-methacryloyl-L-alanine) and poly(N-methacryloyl-L-alanine-co-N-phenylmethacrylamide) containing up to 38 mole-% of N-phenylmethacrylamide were synthesized by radical copolymerization. These polymers were characterized by UV and IR spectroscopy and by conductimetric titrations. The samples were then studied by potentiometric titrations in pure water and in aqueous organic solvents, in the temperature range of 5 - 65°C. The experimental results show that, opposite to poly(methacrylic acid), poly(N-methacryloyl-L-alanine) takes no compact structure in water. The insertion of N-phenylmethacrylamide induces the appearance of this compact structure over 15 mole-% of this residue. Thereafter, the stability of the compact structure increases when increasing the amount of N-phenylmethacrylamide. Experimental results suggest that it is due to increasing Van der Waals interactions between the hydrophobic side chains.
    Additional Material: 11 Ill.
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    Lamellar crystalline structure of block copolymers with an amorphous and a crystallizable block: Effect of the nature of the crystallizable block (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 989-995 
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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: Block copolymers of styrene and ethylene oxide (SEO) and of styrene and ε-caprolactone (SCL), in the dry state and in the presence of a preferential solvent of the amorphous block, exhibit a lamellar crystalline structure at temperatures below ≈50°C. In this structure the crystallized chains are folded in two superposed layers. To investigate the effect of the nature of the crystallizable block, two copolymers SEO and SCL of the same relative molecular mass and composition were studied by X-ray diffraction and differential scanning calorimetry. It is established that the nature of the crystallizable block influences the crystallinity and the number of folds of the crystallized chains and the swelling of the amorphous polystyrene block.
    Additional Material: 4 Ill.
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    Versuche zur umsetzung von methylendiphenolen mit glucosederivaten und zur kondensation von O-phenylglucosidderivatenHerrn Prof. Dr. Gustav Stählin, Universität Mainz, zum 80. Geburtstag gewidmet. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1351-1361 
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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: Attempts to apply known methods of glucosidation to oligo[(hydroxyphenylene)methylene]s were not satisfying. The reaction of 4,4'-dimethyl-2,2'-methylenediphenol (1a) with 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide gave a monoglucoside in 11% yield. A second attempt, the condensation of suitable O-phenylglucoside derivatives was unsuccessful. From a series of O-phenylglucosides (4) only 4-(2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyloxy)benzylbromide could be condensed with O-(4-hydroxymethylphenyl)-2,3,4,6-tetra-O-acetylglucopyranose to the corresponding diglucoside of 4,4'-oxydimethylenediphenol (7). Condensation reactions of the O-phenylglucoside 4k, to obtain an O-glucosidized poly[(hydroxyphenylene)methylene], were accompanied by decomposition. The results showed that the usual methods of the preparation of glucosidized phenols cannot be transferred to oligomeric or polymeric derivatives.
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    The anionic polymerization of 2-pyrrolidone in bulk and in suspension (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1399-1405 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study on the anionic polymerization of 2-pyrrolidone in bulk and suspension under isothermal conditions is described. After a discussion about the disadvantages of the bulk process carried out by using N-potassium-2-pyrrolidone as initiator and N-acetyl-ε-caprolactam as activator, a possible alternative way is proposed on the basis of the suspension polymerization initiated by N-potassium-2-pyrrolidone and activated by silicon tetrachloride. The ultraviolet absorption spectra of the polymer samples obtained by the above methods reveal that undesiderable side reactions leading to degradation of the keto amide groups, are almost negligible under the aforementioned conditions.
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    Changes of molecular weights of thermally exposed polymers (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1441-1447 
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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: Theoretical relations between the change of molecular weights of thermally exposed polymers with arbitrary initial distribution and time have been derived. These relations were used to correlate the changes of molecular weights of thermally exposed polypropylene.
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    Solid phase photoreduction of methylviologen on cellulose (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1111-1118 
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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: Methylviologen (1,1′-dimethyl-4,4′-bipyridinium dichloride, MV2+) absorbed on cellulose paper can be reduced photochemically in solid phase. The ESR spectrum (singlet; g = 1,967, ΔHmsl = 13,5 gauss) shows the photochemical formation of its cation radical (MV•+). The MV•+ formed on cellulose is unusually stable against oxidation by oxygen. Photochemical formation and slow oxidation of MV•+ under air occur fairly reversibly. The concentration of MV•+ and the optical density (O.D.) at 620 nm show a linear relationship. The concentration of MV•+ at 1 O.D. corresponds to 1,07.10-8 spins/cm2 cellulose paper. The formation of carbonyl groups in MV2+/cellulose after irradiation indicates that cellulose acts as electron donor. The mechanism of the solid phase photoreduction is discussed in relation to the effect of other carbohydrates or inorganic materials as adsorbents.
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    A theoretical study on the 1H NMR chemical shift of alanine oligopeptides (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1097-1109 
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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: All the NH and α-CH proton chemical shifts of alanine oligopeptides (Ac-(Ala)n-NHMe, where n = 1-6) with extended and α-helical conformations and anti-parallel β pleated-sheet structure, were calculated by taking into account the magnetic anistropy effect due to the C=O and two kinds of C—N bond anisotropies, and the electric-field effect. The observed spectral behavior of the NH or CH protons in Ac-Ala-NHMe and Ac-(Ala)2-NHMe could be mostly predicted from the calculation, which indicates that the NH and CH chemical shifts in these oligomers are mainly determined by the intramolecular shielding effect. On the other hand, the appearance of the “doublet α-CH peak” for oligomers with chain lengths of five or more reported by Goodman et al. could not be interpreted in terms of the intramolecular shielding effect. In this case, therefore, whether the CH protons are shielded from the solvent or not, seems to be a dominant factor for the origin of the “doublet peak”. The magnetic anisotropy effect of a peptide group was also examined.
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    Polybutadiènes hydroxytéléchéliques, 4.Partie 3: Cr. Fages, Q.-T. Pham, Makromol. Chem. 180, 2435 (1979). Microstructure des polybutadiènes hydroxytéléchéliques radicalaires observée par 1H NMR à 350 MHz et mécanismes de propagation (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1167-1176 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The examination by 1H NMR spectroscopy at 350 MHz of commerical hydroxytelechelic polybutadienes Arco R45M® allows the quantitative determination of the in-chain vinylcentered triads and the 4 types of hydroxylated vinyl chain ends. Vinyl primary radicals as well as macroradicals were found to propagate with penultimate and pen-penultimate effects.
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    Polymérisation anionique de l'acroléine, 2.Partie 1: cf.1. Influence de la nature du contre-ion et de la température sur la cinétique de la réactionTexte de la communication présentée à l'IUPAC de Mainz, septembre 1979. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1215-1227 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In tetrahydrofuran, with Na+ and Li+ as counter-ions, the kinetic order of the anionic polymerization of acrolein is unity for monomer and for initiator. These results indicate that the living ends are not associated at the studied concentrations of initiator. The polymerization rate depends on the nature of the counter-ion. Transfer reactions to monomer do not affect the polymerization rate but greatly change the molecular weights Mn of polyacroleins. The experimental M are much lower than the theoretical M. The propagation constants kpr and the transfer constant hm are determined using these experimental values of M. From these results, we can conclude that with Li+ as counter ion, transfer reactions are much more numerous than with Na+. Furthermore, the polymerization rate increases with temperature. The activation energies of the propagation (Ea,pr) and transfer reactions (Ea,t) can be determined separately. When the temperature increases the propagation reaction is promoted in comparison to the transfer reaction to monomer, and simultaneously transfer reactions to polymer take place. This last phenomenon restricts the upper value of the polymerization temperature.
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    Oxydation photocatalytique des polypropylènes isotactique et atactique (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1229-1241 
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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: By photooxidation of isotactic and atactic polypropylene (PP), irradiated at wavelengths 〉300 nm in air, alcoholic, acidic, ester, lactonic, and unsaturated functions are formed as shown by IR spectrophotometry. The primarily formed hydroperoxy and ketone groups are rapidly photolyzed and their concentrations are kept low. In presence of UV absorbing pigments like TiO2 or ZnO, the same photoproducts are formed with lower rates than in the transparent polymers. In atactic PP, ZnO and TiO2 (rutile or anatase) show different photoactivities. When the light is absorbed in ZnO, accumulation of ketone and lactonic groups is observed. When TiO2 is the absorbing species, oxidation is going further and acidic, ester, and lactonic functions may be observed; TiO2 appears to be able to photocatalyze the disappearance of ketone groups. In isotactic PP of high cristallinity, direct photooxidation and photocatalyzed oxidation are superimposed and differences between ZnO and TiO2 cannot be observed.
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    Effect of solvent on 13C NMR chemical shifts of tetrad methylene carbons of poly(vinyl chloride) (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1243-1251 
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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 13C NMR chemical shifts of tetrad CH2 carbons of poly(vinyl chloride) are observed in solvents covering a wide range of relative dielectric constants and show extreme sensitivity to the solvent. The chemical shifts are interpreted theoretically by means of the solvaton-CNDO/2 MO theory.
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    Synthesis and tumor-inhibiting activity of new heparin-bound nitrogen mustard analogues (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1679-1683 
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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 nitrogen mustard analogues in which bis(2-chloroethyl)-amino groups are separated by oxyethylene groups, 1,14-dichloro-3,12-bis(2-chloroethyl)-3,12-diaza-6,9-dioxatetradecan (3c) and 1,17-dichloro-3,15-bis(2-chloroethyl)-3,15-diaza-6,9,12-trioxaheptadecane (3d), were synthesized by reaction of bis(2-hydroxyethyl)amine (2) with bis(2-chloroethyoxy)ethylene (1a) and with 1,11-dichloro-3,6,9-trioxaundecane (1b), respectively, followed by treatment with thionyl chloride. The analogues were then complexed with heparin. The resulting heparin-complexes show inhibiting activity against transplanted Sarcoma-180 A in mice.
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    Cosolvents of PMMABased on a Communication presented to the IUPAC International Symposium on Macromolecules, Florence (Italy), September 7 - 12, 1980. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1705-1714 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Several cosolvent mixtures for PMMA are reported. Their cosolvency has been confirmed by studying phase separation temperatures as a function of solvent composition. The results show that they are very powerful cosolvents. Acetonitrile forms such cosolvent mixtures with compounds containing different chemical groups (ester, ketone, alcohol, chloroalkane). The mixtures of acetonitrile with alcohols are nonsymmetrical with respect to the solubility parameter value of PMMA. They cannot be explained by simple δ theory. The mixture of formamide with ethanol is also nonsymmetrical and constitutes a true cosolvent pair for PMMA. The associating tendency of the polymer in the single solvent, plus the somewhat ordered structure of the pure liquids, are invoked to suggest that cosolvency is attained by breaking such order and association (in addition to the existence of unfavourable interactions between the cosolvents).
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    Ion-trapping in cationic polymerization, 2.Part 1: cf.1. Relative rates of trapping and relative chemical shifts for structurally differing phosphines as trapping agentsPresented in part at the IUPAC Macromolecular Symposium in Mainz, September 1979. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1735-1742 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The reaction of ethyl trifluoromethanesulfonate with phosphines to form phosphonium salts was used as a model reaction for the “trapping” of the various propagating species by phosphines in the polymerization of THF and other cyclic ethers. In dichloromethane at 25°C, the values of the bimolecular rate constant ktr were determined for various phosphines. For (C6H5)3P:5.10-3 mol-1.l.s-1, for (C6H5)(CH3)2P:0,22 mol-1.l.s-1, for (C6H5)(n-C3H7)-(CH3)P:0,13 mol-1.l.s-1, and for (n-C4H9)3P: 1,3 mol-1.l.s-1. It was found that the ratio ktr/ka (ka is the rate constant of the ethylation of THF by ethyl trifluoromethanesulfonate) changes from 40 for triphenylphosphine to 104 for tributylphosphine. Differences of chemical shifts, measured for various quaternary phosphonium cations differing in one substituent, were observed for ions with various substituents (e.g. based on parent methylpropylphenylphosphine).
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    Einfluß des temperns auf die negative thermische ausdehnung von polyethylen (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1787-1799 
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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 linear thermal coefficient of expansion for high density polyethylene, extended to draw ratios λ = 8 to 16 is α = -24·10-6 K-1 at 20°C. This value results from the orientation of crystallites with an expansion coefficient αc = -12·10-6 K-1 and from stresses in the amorphous phase. Using the model of series coupling of crystalline and amorphous parts the value αam ≤ -50·10-6 K-1 is calculated for a crystallinity xv = 70%. From measurements of Young's modulus the fraction of tie-molecules χtie = 0,4% of the sample is assessed and the expansion coefficient αtie = -90·10-6 K-1. Annealing of the samples leads to shrinkage while the density ρ increases slightly and the expansion coefficient α increases considerably. Samples annealed at temperatures closely below the melting point show a slight decrease of the density at 20°C but a value of α exceeding that of isotropic samples. This effect can be explained by preferred orientation of the crystal a-axis in fibre direction as soon as orientation starts to break down.
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    Long-term change in conformation of macromolecules in solution, 2.Part 1: cf.1. Poly(acrylamide-co-sodium acrylate)sPaper in part presented at the International Symposium on Macromolecules (IUPAC), Florence (Italy) on Sept. 7 - 12th (1980). (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2277-2287 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The solution viscosity of aqueous poly(acrylamide-co-sodiumacrylate)s decreases with time in the scale of weeks. This unusual viscosity loss has been investigated by viscometry and by light scattering on high purity copolymer samples with different ratios of the components.  -  No viscosity loss can be observed in NaCl solution of high enough salt concentration. From the experiments it is concluded that a conformational change causes the viscosity decrease. No chain scission occurs. Light scattering measurements were used to directly confirm this hypothesis.  -  The viscosity loss may be caused by a conformational change of single molecules involving hydrogen bonds and can be interpreted as a transition from a partly stiffer, higher viscous structure to a more flexible one. As the driving force for the conformational change the entropy is discussed. The pronounced time dependence may be interpreted by a cooperative effect of loosening and combining of hydrogen bonds.  -  A similar behaviour has been observed earlier in aqueous poly(acrylamide) solutions. Thus, for some water soluble polymers one has to be aware of a time dependent parameter.
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  • 246
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    Carbon-13 relaxation study of crosslinked gels of poly(methyl methacrylate) (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2289-2295 
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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 motion of covalently crosslinked gels of poly(methyl methacrylate) (PMMA) swollen by benzene-d6 was studied by means of 13C NMR spectroscopy. The dependence of the segmental motion of PMMA on stereosequence was not affected by the presence of the covalently crosslinked part in the chain; isotactic sequence was more mobile than syndiotactic sequence. The spin-lattice relaxation times, T1's, for all the 13C nuclei of PMMA swollen with benzene (benzene content, 90 wt.-%, 0,01 mole-% of crosslinking) were considerably longer than those observed for the linear PMMA (benzene content, 75 wt.-%). Moreover, all the T1 values decreased with increasing of the degree of crosslinking, regardless of the crosslinking agent and reached to the values of T1 observed for uncrosslinked PMMA or to slightly larger values when the content of crosslinking agent was 1 mole-%. However, the nuclear Overhauser enhancement data were essentially independent of the degree of crosslinking within experimental error.
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    Polymérisation anionique de l'acroléine, 3.Partie 2: cf.9. Analyse des microstructures par 1H NMR et 13C NMR et mécanisme de polymérisation (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2321-2342 
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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: We have synthesized anionic polyacroleins using various initiators (naphthalene complex, tert-butyllithium) in different solvents (tetrahydrofuran, toluene). We have studied the 1H NMR and 13C NMR spectra of the polymers and assigned monomeric units and diads by comparison with spectra of four compounds corresponding to the different microstructure arrangements. By this method, we have clearly proved the presence of 1,4- as well as 3,4- and 1,2-units. But numerous cyclisations occur on the 1,2-units. Using only the 1H NMR method, a first estimation of the microstructure was obtained. 13C NMR gave further information and permitted the estimation of the (1,4-cis)/(1,4-trans) ratio. Furthermore the presence of hydroxyl groups along the chains has also been established. A satisfactory determination of the 1,2,3,4- and 1,4-structure percentages of several polyacroleins has been obtained using 1H NMR and 13C NMR simultaneously. A mechanism of acrolein polymerization, based on two different living ends is proposed. The microstructure indicates the existence of several complexation phenomena. When the living end/metal and monomer/metal complexations are weak (with Na+ e.g.), the polymer consists mainly of 1,4- and 3,4-units. On the other hand, with Li+, the microstructure has a high 1,2-content. Moreover, the living end/Li+ complexation would decrease with the chain length, because of the increasing attraction of the cation by the other complexing sites on this chain.
    Additional Material: 9 Ill.
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    Linear oligopeptides, 78.Part 77: cf.1. The effect of the insertion of the proline residue on the solution conformation of host peptides (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2007-2014 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformational properties of three series of monodispersed, chemically and optically pure, PEGThe following abbreviations have been used in the text: PEG, poly(ethylene glycol); -NHPEG, “amino-PEG”; -NHPEG-M, “amino-PEG” -monomethyl ether; t-Boc, tert-butyloxycarbonyl; Z, benzyloxycarbonyl; Ala, alanine; Met, methionine; Gly, glycine; Glu, glutamic acid; Pro, proline; OBzl, benzyloxy; OEt, ethoxy; CD, circular dichroism; MeOH, methanol; TFE, 2,2,2-trifluoroethanol; HFIP, 1,1,1,3,3,3-hexafluoro-2-propanol.-bound linear host oligopeptides of the general formula \documentclass{article}\pagestyle{empty}\begin{document}$ t{\rm - Boc\rlap{--} (L - Met\rlap{--} )}_n {\rm NHPEG} $\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ t{\rm - Boc\rlap{--} (L - X\rlap{--} )}_n {\rm NHPEG - M} $\end{document} [X = Ala, Glu(OBzl)] containing a single guest L-Pro residue at different positions in the main chain have been investigated in aqueous and alcoholic solutions as a function of concentration, temperature, and added salts using CD. The corresponding N-deblocked peptides have also been examined. The incorporation of the L-Pro residue into a host petide chain blocks the extension of the α-helical conformation at the level of the segment containing the guest residue at its N-terminal end. The investigations reveal asymmetric helixnucleation properties of the L-Pro residue as predicted by theory. In β-structure-forming oligopeptides, the insertion of a L-Pro residue results in a significant destabilization of the ordered conformation. Thus, aggregation of peptide chains is less pronounced in these co-oligopeptides.
    Additional Material: 4 Ill.
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    Styrene-divinylbenzene copolymers, 3.Part 2: cf H. Jacobelli, M. Bartholin, A. Guyot, Angew. Makromol. Chem. 80, 31 (1979). Revisited IR analysisThis work is part of a research project. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2075-2085 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A critical analysis of the styrene-divinylbenzene resin infra-red spectra was made using previous works and new results. A method for the determination of pendent double bonds and also crosslinking degree and composition of the resin is drawn. A few examples of application are given.
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    Eine neue methode zur ermittlung kinetischer und kalorischer daten einer radikalischen copolymerisation durch differentialthermoanalyse (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2095-2103 
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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 heats of copolymerization of styrene and methyl methacrylate were measured by means of differential thermal analysis (DTA). Extrapolating the DTA curves to time zero, monomer reactivities and the ratio of the rate constants of termination can be obtained by a new method of evaluation. Calibration is not necessary for this procedure. With calibration, however, the rates and the heats of polymerization can also be measured. The data agree well with those reported in the literature.
    Additional Material: 4 Ill.
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    A novel synthetic route to all-ortho novolac resins (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2151-2159 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A facile synthesis of ortho-linked novolacs was achieved by reaction of selected metal phenolates with paraformaldehyde. Both solvent and phenolate counter-ion play a leading role in the ortho-specific methylene-bridging of the phenolic nuclei. The combined use of highperformance liquid chromatography and 13C NMR spectroscopy proved to be successful in the characterization of these resins.
    Additional Material: 2 Ill.
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    Succinic half-esters of poly(ethylene glycol)s and their benzotriazole and imidazole derivatives as oligomeric drug-binding matrices (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2183-2192 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: α-Hydroxysuccinyl-ω-hydroxysuccinyloxypoly(oxyethylene)s (succinic half-esters of poly-(ethylene glycol)s) (2) of different molecular weights were prepared, and transformed into the corresponding benzotriazole and imidazole derivatives 3 and 4. The benzotriazolyl or the imidazolyl residues in these polymers can easily be exchanged. This was proved with model compounds bearing hydroxyl or amino groups. Polymers of this type may be considered as potential oligomeric drug-binding matrices.
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  • 253
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    Temperature effect on the stereoelective polymerization of methylthiirane in homogeneous phase (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2225-2231 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Chiral cadmium thiolates of cysteine with cyclohexyl or (-)menthyl ester groups were prepared and compared with similar compounds (with isopropyl or methyl ester groups) as initiators for stereospecific polymerization of methylthiirane in homogeneous phase. The resulting polymers are highly isotactic and in all cases stereoelection can be reversed with a small change in polymerization temperature. This temperature effect permitted to differentiate two stages in the polymerization corresponding to the formation of a precursor and to that of a high polymer, respectively.
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    Asymmetric-selective polymerization of (R,S)-α-methylbenzyl acrylate initiated with Grignard reagent/(--)-sparteine and its modified systems (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2737-2746 
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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: Asymmetric-selective (or stereoelective) polymerization of racemic α-methylbenzyl acrylate (2a) was studied with Grignard reagent/(-)-sparteine and its modified catalyst system in toluene. All catalyst svstems polymerized preferentially the (R)-monomer over the (S)-monomer. The Grignard reagent/(-)-sparteine system showed very low activity and gave the polymer only in a few per cent yield at -78°C. The addition of secondary amines such as piperidine and diethylamine to the catalyst system improved not only the activity but also the selectivity. The optical purity of the polymer initially formed with the cyclohexylmagnesium bromide/(-)-sparteine/diethylamine system at - 78°C was 84%, and at about 80% polymer yield almost optically pure monomer was recovered. Asymmetric selectivity decreased with an increase of temperature. The dyad tacticity of the polymer was determined by 1H NMR spectroscopy. There was no clear correlation between the selectivity and tacticity. The role of the amines in the catalyst systems was investigated by 1H NMR spectroscopy.
    Additional Material: 4 Ill.
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    Flow properties of ethylene/vinyl acetate copolymers (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2789-2800 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of linear and branched fractions of an ethylene/vinyl acetate (EVA) copolymer is characterized by viscometry and gel permeation chromatography (GPC) exclusively. Characterization results are applied to the study of the influence of branching on flow properties of concentrated solutions of EVA fractions. Newtonian viscosity-concentration-molecular weight relationships are obtained for both linear and branched samples. Graessley's theory of entanglements for linear polymers is tested with a set of fractions. Experimental flow curves come out to be independent of the linear or branched nature of the samples.
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    The effect of monomer crystal structure on the solid-state polymerization of N-vinylcarbazole (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2351-2357 
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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 solid-state polymerization of N-vinylcarbazole initiated by γ-rays was studied by X-rays, IR and GPC techniques to understand the role of the monomer crystal structure on the polymerization mechanism. From the X-ray diffraction results it was possible to explain the chain growth mechanism and limiting conversion. The molecular weight distribution and the role of oxygen was explained from the GPC results. Liquid chromatography and IR results were used to explain the nature of unpolymerized monomer after reaching the limiting conversion. It was proved that the unpolymerized monomer retains its crystal structure and does not react to any other compounds.
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    Oxidative polymerization of 2,6-bis(3-methyl-2-butenyl)phenolDedicated to Professor, Dr. Georg Manecke on his 65th birthday (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2361-2369 
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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: Oxidative polymerization of 2,6-bis(3-methyl-2-butenyl)phenol (1) was carried out by copperpyridine catalyst. 1 was oxidatively polymerized to yield poly[oxy-2,6-bis(3-methyl-2-butenyl)-1,4-phenylene] (2) in a similar manner as it has been observed for 2,6-dimethylphenol (3a). 2 is an oily material with a degree of polymerization of 6,2. 1 and 3a copolymerized with similar reactivity to form the copolymer 4 (degree of polymerization 16 to 29). The 3-methyl-2-butenyl groups in the polymer show enough chemical reactivity for an addition of bromine or graft-polymerization.
    Additional Material: 5 Ill.
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    Untersuchung der grignard-wurtz-reaktion von partiell hydrobromiertem 1,4-polybutadien und partiell α-bromiertem polyoctenylen durch metathese-abbau der polymere und identifizierung der niedermolekularen produkteHerrn Prof. Dr. Dr. h. c. F. Patat zum 75. Geburtstag gewidmet (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3041-3052 
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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: Partially hydrobrominated 1,4-polybutadiene and α-brominated polyoctenylene were treated with pentyl, isopropyl, cyclohexyl, benzyl, 4-methylbenzyl, phenyl, 4-methylphenyl, 4-ethylphenyl, 3,4-dimethylphenyl, 2,4,6-trimethylphenyl, 4-chlorophenyl, 4-fluorophenyl, 4-methoxyphenyl, 3,4-dimethoxyphenyl, and 2-thienyl magnesium bromide. In addition partially hydrobrominated 1,4-polybutadiene was treated with 2-methylbenzyl, 3-methylbenzyl and 4-isopropylphenyl magnesium bromide. Polymers were degraded by metathesis with 4-octene using WCl6/(CH3)4Sn as a catalyst. The low molecular products were separated by gas chromatography and identified by mass spectrometry. Mass spectra of products with 4-alkyl(aryl)octanediylidene units (from modified polybutadiene) and 2-alkyl(aryl)octanediylidene units (from polyoctenylene) were compared.
    Additional Material: 6 Ill.
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    13C NMR sequence analysis, 20Part 19: H. R. Kricheldorf, H. Sekiguchi, B. Coutin, J. Polym. Sci., Polym. Chem. Ed. submitted.. Stereospecificity of the polymerization of D,L-Leu-NCA and D,L-Val-NCAN-Carboxyanhydrides (Oxazolidine-2,5-diones). (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3077-3098 
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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 copolymerization of D- and L-Leu-NCA as well as that of D- and L-Val-NCA was studied under various conditions. Even nonpolar solvents, such as diethyl ether or ligroin, used for the precipitation of the poly(D,L-amino acid)s, were found to have an influence on yield and tacticity of the isolated polypeptides indicating that atactic polypeptides of low molecular weight may be soluble in these solvents. 13C NMR spectra of the isolated poly(D,L-amino acid)s were measured in trifluoroacetic acid and the carbonyl signals were used for the evaluation of the teacticity. Under all reaction conditions only a moderate degree of stereospecificity was found. D,L-Leu-NCA initiation with protic nucleophiles, such as benzylamine or diethylamine, favors the formation of isotactic blocks. In the case of D,L-Val-NCA again isotactic blocks are slightly favored if benzylamine is used as initiator, while diethylamine, like other strong bases, causes preferred formation of syndiotactic sequences. With strong aprotic bases and electrophilic cocatalysts, i.e. under conditions favoring the “activated monomer mechanism”, the highest degrees of stereospecificity were observed. However, in the case of D,L-Leu-NCA isotactic blocks are predominantly formed, while in the case of D,L-Val-NCA syndiotactic blocks are favoured. Changing the solvent may result in a reversal sense of the stereospecificity. The absence of long isotactic blocks in all samples of this work was also demonstrated by the good solubility of all samples in various organic solvents.
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    Copolymers of 2-acrylamido-2-methylpropanesulfonic acid and aromatic vinyl compounds as potential media for photosensitized electron transfer reactions (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3135-3147 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In an expectation as potential media for photosensitized electron transfer reactions, polymers carrying both strong electrolytic and hydrophobic segments were prepared by the copolymerization of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and styrene. The AMPS segments were found to have a remarkable power to solubilize the hydrophobic segments into water, i.e., even a copolymer with a styrene mole fraction of 0,72 is still soluble in water. Salt effect on the reduced viscosity, broadening of NMR spectra in D2O, and enhanced excimer fluorescence of styryl groups in aqueous solution indicated a pronounced hydrophobic interaction of a number of styryl groups along the chain in the copolymer with high styrene content. 8-Anilinonaphthalene-1-sulfonic acid, 1,6-diphenyl-1,3,5-hexatriene, and a cyanine dye were used as fluorescent probes for the hydrophobic microdomains. The results suggested that the microdomains are highly hydrophobic in nature but less capable to solubilize the fluorescent probes than the surfactant micelles. An electron microscopic image of the copolymer was also discussed as a supporting evidence for the presence of microdomains.
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    Internal mobility of PMMA in concentrated CDCl3 solutions, 1. 1H NMR spectra (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3169-3176 
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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: Measurements of the second moment and analysis of the derivative shape of 1H NMR spectra of PMMA have shown that in CDCl3 solutions containing 60% (w/w) or more of polymer, the internal mobility of PMMA is similar to the mobility of the pure polymer. The main chain is rigid on the NMR scale, and only CH3 groups are mobile. The motion of CH2 groups, representing the segmental mobility of the backbone chain, becomes appreciable on the NMR scale at concentreations of 60-50%, depending on the temperature. Measurements of 1H MAR-NMR spectra of solutions containing 30% or more of polymer indicate spatial anisotropy of internal motions of PMMA. This spatial anisotropy is probably due to intermolecular interactions of ester groups, similarly as in the gels of the PMMA stereocomplex.
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    Die molekulargewichtsverteilung bei der kontinuierlichen anionischen polymerisationHerrn Professor Dr. Dres. h. c. G. V. Schulz mit den besten Wünschen zum 75. Geburtstag gewidmet (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3207-3221 
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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: Equations are given for the continuous anionic polymerization in a tubular reactor which describe the resulting molecular weight distribution as a function of the size of the mixing zone and of the concentration of chain terminating impurities in the solution of the monomer. Polymerization of styrene and of butyl methacrylate was conducted with different initiator concentrations, and the size of that part of the reactor where backmixing occurs was estimated from the molecular non-uniformity of the polymers, whereas the degree of polymerization allows the determination of the concentration of the impurity. This latter quantity apparently increases with initiator concentration in the case of methacrylate polymerization and therefore suggests a reaction of the initiator with the ester group to occur. The shape of the molecular weight distribution indicates termination of the growing methacrylate chains, possibly by reaction of living chain ends with ester groups.
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    Elementarprozesse löslicher ziegler-katalysatoren. Polymerisationskinetische analyse und mathematische modellierung im system Cp2TiPropylCl/AlEtCl2/ethylenHerrn Prof. Dr. Dr. h. c. Franz Patat zum 75. Geburtstag in Verehrung gewidmet (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3265-3278 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper deals with the kinetics of the polymerization of ethylene catalysed by the soluble Ziegler-catalyst Cp2TiPropylCl/AlEtCl2. By means of a special method it was possible to study the kinetics of the initial instationary homogeneous part of the polymerization. The dependences of the initial rates on the catalyst components prove that the polymerization active species is formed in two successive very dynamic equilibria. The primary complex equilibrium is entirely located on the right hand side, whereas the second equilibrium depends considerably on the ratio of the catalyst components and is shifted on the active species side only at very high Al/Ti ratios. Because of this location of the two successive equilibria the dependence of the polymerization velocity vp on the charged Al concentration (that is, the Al isotherm) has to show a sigmoidal curve course in the inital part, which experimentally is confirmed exactly. Finally, this extensive kinetical analysis leads to the complete reaction scheme of the polyreaction and by mathematical modelling to the quantitative calculation and description of the experimental curves and dependences (e.g., Al-isotherm).
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    Thermomechanical analysis of linear aromatic polyesters (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3323-3330 
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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 thermomechanical properties of linear aromatic polyesters, studied using thermomechanical analysis techniques, have been related to the chemical structure and methylene chain length. An increase in the number of methylene groups, the use of an asymmetric diacid, or random copolymerization of the repeating units of these polyesters, resulted in a lower linear thermal expansion coefficient α, a lower Vicat softening temperature Ts, a lower heat deflection temperature Td, and a lower glass transition temperature Tg. With longer methylene sequence lengths, the influence of the methylene groups on the thermomechanical properties is predominant, the data are closer together. The values are generally highest for the terephthalate series and lowest for the copolymer series. Glass transition temperatures calculated from group contributions and measured experimentally agreed. The deflection temperatures approximated the glass transition temperatures and the Vicat softening points the melting temperatures.
    Additional Material: 6 Ill.
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    Phase distribution chromatography (PDC) as a method for the investigation of polymers in solution, 2Part 1: Cf.1.. Flow-equilibrium (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2845-2861 
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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 dynamical region of the measured calibration curves is investigated using the results of the theory published previously. The kinetic constants of the flow-equilibrium are calculated from the measurements according to two different models for a spontaneous polymer diffusion of the transported P-mer from sol into gel of the Phase Distribution Chromatography (PDC)-column. The corresponding lateral concentration profiles in the gel are found by analytical integration of Fick's second law under the corresponding boundaries. An energetic model of this flow-equilibrium is stated, giving the activation enthalpy and -entropy of the rediffusion of the polymer from gel into sol after some retardation time in the gel. The influence of the gel mass of the column on its resolution is briefly investigated. Since the measurements show that the resolution of the PDC-column vanishes in the vicinity of the theta point, spreading phenomena in the column can be investigated by means of analysis of the corresponding PDC elution curves. The results give a basis for the numerical computation of the molecular weight distribution of narrowly distributed polystyrenes from PDC elution curves at sufficiently low column temperatures. The PDC-separation effect is opposite to that of gel permeation chromatography (GPC).
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021821029
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    Lösungseigenschaften methyl- und chlorsubstituierter Bisphenol-A-PolycarbonateHerrn Prof. Dr. Grünewald zum 60. Geburtstag gewidmet (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2873-2879 
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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: Solution properties of dilute polymer solutions are studied for polycarbonates from 3,3′,5,5′-tetramethylbisphenol A, from 3,3′-dimethylbisphenol A, from 3,5-dimethylbisphenol A, and from 3,3′,5,5′-tetrachlorobisphenol A in regard to the influences of the different methyl and chloro substitutions. The Mark-Houwink relationships are established in dichloromethane at 25°C. The unperturbed dimensions, evaluated from viscosity data using the Burchard-Stockmayer-Fixman method, are compared with those for bisphenol A polycarbonate. The unperturbed end-to-end distances are increased by the methyl and chloro substituents. The flexibility factors, calculated on the basis of the unperturbed dimensions and the dimensions of the freely rotating chain, indicate a greater rigidity of the polymer chain of the methyl and chloro substituted polycarbonates.
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    Polymers containing enzymatically degradable bonds, 4Part 3: cf.3. Preliminary experiments in vivo (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2941-2949 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Copolymers of N-(2-hydroxypropyl)methacrylamide containing oligopeptidic sequences either in side chains or as part of crosslinks were prepared. These polymers were applied intravenously to rats, and spectrophotometric analysis (oligopeptidic side chains) or gel permeation chromatography of urine (oligopeptidic crosslinks) have shown that both types of polymers are cleavable in vivo.
    Additional Material: 5 Ill.
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    Uncatalysed phenol-formaldehyde reactions. A convenient synthesis of all-ortho novolac resinsCf.:1 (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2973-2979 
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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 uncatalysed reaction between phenol and paraformaldehyde in aprotic nonpolar media at 170-220°C provides an efficient inexpensive route to novolac resins with almost all of the methylene-linkages in ortho-ortho′ sequence. The role played by the solvent is shown to be determinant in the ortho-specific insertion of methylene-bridges between the phenolic units.
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    The structure of poly(N-vinylcarbazole) obtained with cationic initiators and electron acceptors as catalysts (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3003-3015 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(N-vinylcarbazole)s, [poly(l-(N-carbazolyl)ethylene)s], (PVCz's) were prepared under various polymerization conditions. The stereoregularities were estimated by means of 13C NMR spectroscopy. Although the stereoregularity of the polymers obtained by BF3O(C2H5)2 was hardly changed by the polymerization temperature, it changed with the solvent polarity from an isotactic-rich configuration in toluene and CH2Cl2 to a syndiotactic-rich configuration in nitrobenzene. The 13C NMR spectra of the polymers obtained by organic electron acceptors, support the conclusion that the polymerization by tetracyanoethylene, p-bromanil, 2,3-dichloro-5,6-dicyano-p-benzoquinone, and tetrachlorophthalic anhydride proceed by a cationic mechanism. In the polymerization of N-vinylcarbazole (VCz) with maleic anhydride as an electron acceptor, a small amount of copolymer was obtained together with the homopolymer of VCz. Although the structure of the homopolymers is the same as that of the radically obtained polymer, it is considered that the polymer is formed by a cationic mechanism. The polymerizations of VCz by inorganic compounds, such as ferric nitrate, cupric nitrate, cupric bromide, etc., as catalysts are cationic.
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    Etude de radicaux libres forméas par irradiation ultraviolette de l'amidon: Application aux réctions de photodégradation et de photogreffage (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3053-3068 
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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: General investigations of radical processes in starch were carried out. ESR experiments showed that UV irradiation of starch, both in photosensitized and unphotosensitized experiments, results in chain scission and radical generation on the glucosidic ring. It was shown that benzophenone, deoxybenzoin and derivatives (2a-d) are efficient sensitizers. The ESR spectra were interpreted by assuming superposition of three signals; they were ascribed to radicals formed by chain scission and hydrogen abstraction. In addition photodegradation processes of starch in the presence and absence of photosensitizers were investigated. The amount of chain scissions was followed under various experimental conditions and appeared as a function of the initiator. Moreover, oxygen was shown to enhance the yield of chain scissions: this was explained through the formation of peroxide functions at C1-position. UV light induced grafting of a vinyl monomer onto starch was also investigated. It appeared that chemical grafting can easily be achieved through a radical reaction. Moreover, the percentages of grafting and degradation were strongly dependent on the photoinitiator. The whole results gave the possibility to select an efficient initiator of the grafting reaction. In the case of methyl methacrylate, α,α-dimethoxydeoxybenzoin (2a) appears to be the most efficient initiator. However, previous works as well as the present work suggest that the grafting efficiency is strongly dependent on the three components: substrate, monomer, and initiator.
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    Electric dipole moment of ethylcellulose, in 1,4-dioxane and in benzene (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3109-3117 
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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 electric dipole moments per repeating unit of ethylcellulose (EC) of various molecular weights were determined by dielectric measurements at 1 kHz (μL) and at 1 MHz (apparent moment, μH) in 1,4-dioxane and benzene. The numerical values were μL = 5,23 D (= 17,45.10-30 C·m) and μH + 2,72 D (= 9,07.10-30 C·m) for 1,4-dioxane, and μL = 4,81 D (= 16,04.10-30 C·m) and μH = 2,42 D (= 8,07.10-30 C·m) for benzene, respectively. μL and μH were almost independent of the molecular weight in both solutions. The persistence dipole moment μq was estimated to be 13,6 D (= 45,36.10-30 C·m) in 1,4-dioxane, and 13,4 D (= 44,70.10-30 C·m) in benzene, respectively, and the flexibility of the EC chain was discussed.
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    Hot drawing of surface growth polyethylene fibers, 2Part 1: cf.2. Effect of drawing temperature and elongational viscosity (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3351-3359 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A distinct improvement of the tensile properties of “surface growth” polyethylene fibers can be realised by drawing at elevated temperatures. The optimal drawing temperatures were found in the range of 120-150°C. Drawing in the hexagonal phase above 150°C does not lead to an increase of strength. Elongational viscosity measurements revealed extremely high values in the order of 1011-1012 Poise. Activation energies between 75-95 kJ/mol were determined from the temperature dependence of elongational viscosity. The observed drawing behaviour is discussed in relation to the morphological changes that occur during drawing.
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    The synthesis of stereoregular polymers by vinyl, ring-opening, and condensation polymerization reactions (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 4 (1981), S. 47-59 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The important factors which control the stereochemistry of polymerization, and thereby the crystalline properties of the polymers so formed, are considered for four different types of reactions including: (1) the cationic polymerization of substituted α-methylstyrenes to form syndiotactic polymers; (2) the anionic ring-opening polymerization of substituted β-propiolactones to form crystalline polyesters; (3) the metathesis ring-opening polymerization of 1,5-cyclooctadiene to form poly(1,3-butadiene)s of controlled cis-trans contents; and (4) the condensation polymerization of α-methylbenzyl chloride to form isotactic poly(α-methylbenzyl).
    Additional Material: 5 Ill.
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    Sequence regulation in spontaneous binary and ternary copolymerizations via zwitterion intermediates (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 4 (1981), S. 73-84 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper is concerned with the sequence regulation of monomeric units in a series of binary and ternary copolymerizations which proceed without any added catalyst or initiator. The binary copolymerization is consisted of the combination of a nucleophilic monomer (MN) and an electrophilic monomer (ME). The interaction between the two monomers generates a zwitterion of a 1:1 adduct, which is the key intermediate in the copolymerization producing 1:1 alternating copolymer. The varieties of MN and ME monomers, the structures of key intermediates of zwitterions, and the schema of copolymerizations have been discussed. In addition, the “Sequence-Ordered 1:1:1 Terpolymerization” (producing terpolymers of a type .…ABCABCABC….) and “2:1 Binary Copolymerization” (producing copolymers of a type of .…ABBABBABB….) are described, which have been developed on the basis of the above binary 1:1 alternating copolymerization.
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    Mismatched bases in nucleic acids: their effects on structures and stability (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 4 (1981), S. 143-153 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of ribo- and deoxyribo-oligonucleotides were synthesized with the sequences CAnG, CUmG AND CTmG (n and m = 5 or 6). These molecules can form RNA, DNA and hybrid double stranded helices containing either perfect base pairing (n = m), or mismatches (n ≠ m). The thermodynamics of formation of these helices has been measured and the destabilization caused by an extra uridylic, thymidylic or adenylic residue has been determined. Nuclear magnetic resonance of exchangeable imino protons has been used to study the conformations of the different helices. The binding of ethidium to the helices has been studies.
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    Morphology and viscoelastic properties of isotropic and oriented polypropylene films (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 4 (1981), S. 207-222 
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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 physical structure of semicrystalline polymers influences many of their properties. It has been shown that thermal treatment (rate of cooling and annealing) as well as the action of mechanical forces (drawing) of isotactic polypropylene (PP) resulted in materials with different mechanical properties. In the case of isotropic films the crystallization temperature or annealing temperature from the glass and consequently morphological structure which has been formed, determine the values of modulae, yield stress and viscoelastic properties. Reoptical behaviour has been found to be sensitive to structural differences too. The structure and mechanical properties of highly oriented PP samples which have been obtained by drawing through a flat die have been found to be dependent on parameters characterizing this process (drawing rate, apex angle of die and elongation ratio).
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    Catalytic behaviour of metalcomplexes immobilized in functional polymeric carriers (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 5 (1981), S. 121-154 
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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 general principles of construction of gel-immobilized catalyst systems (GICS) are reported as well as some peculiarities of the polymerization of ethylene and of the dimerization of ethylene and propylene in the presence of these systems.GICS consist of a transition metal complex and a specially designed polymeric support. Advantages offered by gel-immobilized catalyst systems are discussed with respect to homogeneous and microheterogeneous metal complex catalysts.
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    Polymerization of epoxides catalysed by metalloporphine (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1073-1079 
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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 catalyst system obtained by the equimolar reaction of diethylaluminium chloride with α,β,γ,δ-tetraphenylporphine exhibits high catalytic activity in the polymerization of propylene oxide to give a polymer with a narrow molecular weight distribution. Average molecular weight of the polymer can be controlled by the initial mole ratio of propylene oxide to catalyst or by the conversion. Ethylene oxide also produces a polymer having a narrow molecular weight distribution.
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    The influence of molecular interaction on polymerization, 5.Part 4: H. Boudevska, C. Brutchkov, V. Veltchev, Eur. Polym. J. 15, 907 (1979). Copolymerization of benzyl methacrylate with maleic anhydride (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1119-1125 
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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: Copolymerization of benzyl methacrylate (BMA) with maleic anhydride (MA), initiated by 2,2′-azoisobutyronitrile at 70°C in chloroform or acetonitrile, were investigated. The complex formation between the two monomers in chloroform was studied by 1H NMR spectroscopy. The stability constant of the complex was found to be 0,25 l.mol-1. The following copolymerization reactivity ratios were found: in chloroform: rBMA = 0,188 ± 0,035 and rMA = 0,003 ± 0,005, in acetonitrile: rBMA = 0,116 ± 0,093 and rMA = 0,231 ± 0,027. By 1H NMR investigations it could be shown that the results correlate with the changes of the reactivity ratios depending on the solvent used.
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    1H and 13C NMR studies on N-acetyl-L-alanyl-L-alanine-methylamide (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1153-1165 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 1H and 13C NMR spectra of N-acetyl-L-alanyl-L-alaninemethylamide and N-acetyl-L-alanyl-L-alanine methyl ester were measured in [2H]6-dimethyl sulfoxide and deuteriochloroform/trifluoroacetic acid solutions. The assignments of the N-terminal and internal NH proton peaks of the amide could be made by means of deuterium exchange experiments in [2H]6-dimethyl sulfoxide solution. An association model of the amide with an antiparallel β-sheet structure was proposed by taking into account the presence of an IR absorption at 1 690 cm-1 as amide I band and the results of the measurement of 3JHN-CαH coupling constants, as well as the deuterium exchange experiment. Moreover, the interaction between the peptide units in these two compounds and trifluoroacetic acid seems to be weaker than the N-acetyl-L-alaninemethylamide-acid interaction in a deuteriochloroform/trifluoroacetic acid solvent system of the same concentration.
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    Copolymères du chlorure de vinylidène avec l'acrylonitrile, le chlorure de vinyle et le méthacrylate de méthyle, 2.Partie 1: cf.4. Fusion  -  utilisation d'un modèle de simulation (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1207-1214 
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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 melting point depression in vinylidene chloride copolymers, when introducing an increasing number of units B = vinyl chloride, acrylonitrile or methyl methacrylate is studied in this paper. A Monte-Carlo simulation model of chains growing and crystallization is applied and allows to know the proportion Xc of defects in the crystalline phase. An equation given by Sanchez is then applied, and the excess energy ε of the defect created by the incorporation of a B unit in the crystalline vinylidene chloride lattice is calculated.
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    Time resolved small angle scattering during isothermal crystallization of unoriented poly(ethylene terephthalate) using synchrotron radiation (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1263-1269 
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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 time course of the small angle scattering pattern of amorphous poly(ethylene terephthalate), (PET), was measured during isothermal crystallization using synchrotron radiation. The samples were heated to temperatures between 117 and 145°C in an oven placed in the path of the X-ray beam. The scattering curves were measured within 10 s at intervals of 1 s so as to follow the kinetics of the process continuously. It appears that the distance between the centres of mass of the crystallites decreases with increasing crystallization time as in oriented PET. The integrated small angle scattering follows approximately the same time course as the increase in the degree of crystallinity during an isothermal crystallization yielding Avrami exponents between 5 and 7. Guinier plots of the low angle region show that the scattering can be attributed to rod-like particles.
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    Substituted and branched polychalcones. Syntheses and characterization by spectrometric methods (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1307-1317 
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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: Polychalcones 4a, b were prepared by a Friedel-Crafts acetylation of vanillin (3a) and p-hydroxybenzaldehyde (3b) and by a Fries rearrangement of the acetates in nitrobenzene using AlCl3 as catalyst. The reaction was carried out in one step under a variety of reaction conditions (time and temperature). The polymers were characterized by UV, IR and 1H NMR spectroscopy. The polychalcones obtained from p-hydroxybenzaldehyde had a limited solubility, but they swoll in DMSO and in dilute NaOH.
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    Thermal decomposition of flame retardant acrylonitrile polymers, 2Part 1: cf.1.. Effect of red phosphorus (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1301-1306 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Elemental red phosphorus was found to be an efficient flame retardant for poly(acrylonitrile) homopolymer (PAN) and, to a lesser extent, also for a modified acrylic resin containing 36 wt.-% of vinylidene chloride (VC2) as comonomer. The data collected show that condensedphase and gas-phase mechanisms are both responsible for the flame inhibition effect of red phosphorus on PAN. On the contrary, a gas-phase mechanism seems to be responsible for the flame inhibition effect of red phosphorus on the AN-VC2 copolymer. Flash-pyrolysis GC data, with pyrolysis products MS identification, are reported for both polymers studied.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820501
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    Syntheses of diacetylene monomers from N-(nitrophenyl)amine substituted diacetylene alcohols (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1363-1370 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several new classes of asymmetric diacetylene monomers of the type O2N—Ar—NH—CH2—C=C—C=C—CH2—R have been synthesized from nitroaniline diacetylene alcohols. The solid state polymerization behavior of several members of these classes has been examined.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820507
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  • 286
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    Hydrogenation of alkenes, alkynes, and other substrates catalyzed by polymeric Pd(II) complexes of 2,3,6,7-octanetetraone tetraoxime (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1385-1390 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Coordination polymers prepared from 2,3,6,7-octanetetraone tetraoxime and bis(benzonitrile)palladium dichloride catalyzed the hydrogenation of alkenes, alkynes, carbonyl compounds, azobenzene and other substrates with some selectivity. The catalytic activity and selectivity were dependent on the palladium content in the complex.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820510
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    Die emulsionscopolymerisation von tetrafluorethylen mit propylen bei niedrigen temperaturen (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1429-1439 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Tetrafluoroethylene and propylene were copolymerized in emulsion at low temperatures (≈25°C) by use of a redox catalyst containing ammonium peroxodisulfate, ferrous sulfate, ethylenediaminetetraacetic acid (EDTA) and hydroxymethane sulfinate. The kinetical study suggested that the working mechanism of the catalyst conforms the following scheme: where the reduction of the ferric ion seems to be rate determining (i.e. k1 ≫ k2) and the hydroxyl ion plays an important role. The overall polymerization reaction is supposed to proceed according to the Case I of the Smith-Ewart theory under the experimental conditions examined.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820515
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    1H and 13C NMR spectra of poly(propyl α-bromoacrylate) and poly(methyl α-bromoacrylate) (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1449-1458 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The 13C NMR spectra measured at 25 MHz of the methyl and propyl esters of isotactic and syndiotactic poly(α-bromoacrylate) were sufficiently resolved to be analysed for pentad tacticity sequences. The pentad tacticity of the syndiotactic polymers prepared with free radical initiators at -40°C agreed with those calculated for Bernoullian sequence distributions based on Pr values of 0,83-0,87. The tacticities of the isotactic polymers prepared with heterogeneous catalysts were determined on the basis of these assignments. Good internal consistency was obtained between the calculated and observed pentad proportions from the quaternary and carbonyl carbon peaks in the spectra of these polymers. The order of chemical shifts for the meso and racemic dyads and tetrads in these polymers were opposite to those found in the equivalent methacrylate polymers, but as with the latter, the 13C-T1 values were longer in the isotactic than in the syndiotactic polymers.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820517
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    Micellisation de copolymères séquencés polystyrène-polyvinylpyridinium, 3Partie 2: cf.2; les résultats présentés dans cet article font partie de la thèse d'état de J. Selb, Université L. Pasteur, Strasbourg (1978).. Influence de la concentration en sel et de la température (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1513-1524 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of the salt concentration and temperature on the micellization phenomenon of polystyrene-poly(4-vinyl-N-ethylpyridinium bromide) block copolymers in dilute solution are investigated in solvents selective for the polyelectrolytic part (water-methanol-LiBr mixtures). The polystyrene moiety being in non-solvent media remains rather collapsed whatever temperature and salt concentration. On the contrary, the latter parameters modify strongly the conformation of the soluble polyelectrolytic chains and therefore determine the “quality” of the solvent essentially towards the polyvinylpyridinium blocks. Consequently an increase of the temperature or a decrease of the salt concentration have the same effect on the behaviour of the copolymers. In the case of a copolymer with a small molecular weight polystyrene block (Mw = 2 700), the unimer-multimer (single molecules/micelles) equilibrium is easily shifted in favour of the single molecules by increasing the temperature or decreasing the ionic strength. On the contrary, if the polystyrene moiety is longer (Mw = 6 000 - 13 000) the micellar weight of the system is little or even not at all influenced by the ionic strength and the temperature. These results emphasize that, for the investigated systems, it is the “insoluble” blocks which essentially govern the micellization phenomenon.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820522
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  • 290
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    Nuclear magnetic resonance studies on polymer carbanions, 2Part 1: cf.2.. Model compounds for α-methylstyrene and α-methylstyrene tetramer dianions (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1533-1540 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 1H and 13C NMR spectra of model compounds for the poly-α-methylstyryl anion, 2-lithio, 2-potassio, and 2-cesio-2-phenylbutane, were determined. The lithium compound had a higher charge density at the α-carbon and a lower charge on the phenyl ring than the other compounds and exhibited phenyl ring rotation at higher temperatures. The activation energy was calculated to be 61, 0 kJ/mol. The potassium and cesium compounds did not show phenyl ring rotation at 80°C. Quantum chemical calculations indicated that the larger cations interact with the phenyl ring especially with the ortho carbons. 13C NMR spectra of α-methylstyrene tetramer dianion with sodium and potassium as counter cation were also measured and compared with those of the model compounds.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820524
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    Thermally initiated emulsion polymerization of styreneHerrn Prof. Dr. Ing. H. Hahn zum 65. Geburtstag gewidmet (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1553-1565 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal polymerization of styrene in emulsion was studied by determination of the number of particles, the rate of polymerization, and the average molecular weight of the polymer formed as a function of the emulsifier concentration. For the number of particles the relation N ∼ [E]1,4 was found, whereas the rate of polymerization showed a dependence of vbr ∼ [E]0,7, only up to an emulsifier content of 0,2 mol. dm-3, but remained constant at higher concentrations. A transfer of low molecular weight radical species from the organic to the aqueous phase is discussed as a prerequisite of polymerization in the latex particles. The deviations from the Smith-Ewart theory are explained by the low rate of radical formation, which does not provide a constant radical concentration per particle.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820526
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  • 292
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    Polymerization of L-leucineN-carboxyanhydride with 1,6-hexanediamine as initiatorHerrn Prof. Dr. Dr. h.c. F. Patat zum 75. Geburtstag gewidmet (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1617-1628 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: L-Leucine N-carboxyanhydride was polymerized in N,N-dimethylformamide (DMF) or 1,4-dioxane (DIO) at 25°C with either 1,6-hexanediamine (1) or its monocarbamate 2 using a constant volume apparatus, initially filled with nitrogen or carbon dioxide. Number average molar masses from amino end group titrations on one hand and from initial monomer/initiator ratios and conversions on the other were practically identical for monomer conversions between 25 and 79%, indicating both the living nature of the polymerization and a participation of all initially present amino groups, despite the fact that polymer precipitation was observed at higher conversions for all systems and an additional precipitation of the carbonate 2 for the system 1/DIO/CO2 at low conversions. Two kinetic stages were observed for the latter system, but three kinetic stages for all other ones. The absence of a rapid initial polymerization period for the system, 1/DIO/CO2 as contrasted to the high initial rates for the systems 1/DMF/CO2 or 1/DMF/N2 points towards a carbamate mechanism in the first case and an amine mechanism in the second. The relation between intrinsic viscosities and number average molar masses of poly(L-leucine) in trifluoroacetic acid at 25°C was found as [η] = 0,0169 〈Mn0,86 ± 0,04 ml/g.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820602
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    Diels-Alder reaction of a trace amount of styrene with cyclopentadiene in a liquid phase (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1669-1677 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: With the intention to prove the possibility of applying the Diels-Alder reaction to trap a trace amount of residual styrene monomer in polystyrene, a model reaction between cyclopentadiene with styrene in a dilute o-chlorobenzene solution was carried out. In the presence of an excess amount of dicyclopentadiene, the consumption of styrene was measured with time lapse by means of gaschromatography. At temperatures ranging from 140 to 220°C, the amount of styrene was observed to decrease remarkably until it reached an equilibrium concentration. The higher the temperature was, the higher the equilibrium concentration became. The equilibrium constants at each temperature and the activation energy for the reaction were calculated.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820607
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    HIO4-oxidized soluble polysaccharides as polyfunctional links for covalent binding of enzymes, 1. Preparation of polysaccharides and matrices for their binding (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1641-1648 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Soluble hydrophillc polyaldehydes can be used as linking and crosslinking reagents for the modification and immobilization of proteins. An imine bond (or possibly an α-hydroxyamino bond) between NH2 functions of proteins or matrices and the aldehyde functions of the soluble polymer is formed under mild conditions. The polyaldehydes used were HIO4-oxidized soluble polysaccharides of different degrees of oxidation, and the NH2 matrices were Enzacryl AA and Enzacryl AH (for reference purposes also aminohexylcellulose), macroporous copolymer of glycidyl methacrylate reacted with ammonia, and nylon 6 and Estapor latices both with surface amino groups. Dextrans and Zulkowski starch were readily oxidized with HIO4, the degree of oxidation being determined by means of a modified photometric aldehyde determination method. As regards the reaction of the matrices with the polyoxidized polysaccharides (“glycosidation of the matrix”), it was found that 20 h incubation at 20°C and phosphate buffer pH = 6 furnished good results. In the investigations discussed in the present paper, relatively large quantities of polysaccharide were used for incubation, in order to achieve a high degree of glycosidation. For a closer analysis of matrices, several methods for the determination of the NH2 concentrations on matrices were examined; in this case the reaction with pentafluorobenzaldehyde in aqueous phase followed by fluoride-analysis furnished well reproducible results.
    Additional Material: 4 Tab.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820604
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    SynthèSe de copolymères triséquencés polybutyramide-polystyrène et polybutyramide-polyisoprène (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1695-1704 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The synthesis of triblock copolymers with crystalline outer blocks of polybutyramide and a central block of polystyrene or polyisoprene was performed. First polystyrene (or polyisoprene) fitted at both ends with acyllactam functions were obtained. In a second step these endstanding functions promote the lactame polymerization to yield the polyamide blocks. A careful characterization of the resulting samples was carried out. The behaviour of these block copolymers is typically that of a thermoplastic elastomer, whereby the crystalline blocks constitute the physical crosslinks in the samples.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820610
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    Living anionic stereospecific polymerization of 2-vinylpyridine, 2.Part 1: cf.1. Kinetics of polymerization and nature of active centres (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1743-1750 
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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 kinetic study of the propagation reaction and the viscosity measurements on solutions of active centres indicate that the living stereospecific polymerization of 2-vinylpyridine initiated by organomagnesium compounds in hydrocarbon solvents, proceeds through unsymmetrical non-aggregated ion pairs. Cryoscopic measurements on a model compound of the active centres, indicate the lack of aggregation which is attributed to the complexation of the magnesium cation by the last and the penultimate pyridine ring of the living polymer chain.
    Additional Material: 5 Ill.
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    Determination of the number-, weight-, and z-average dimensions of macromolecules by viscosity and GPC measurementsHerrn Prof. Dr. Dres. h. c. G. V. Schulz mit herzlichen Glückwünschen zum 75. Geburtstag gewidmet (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1761-1774 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular weight averages are calculated which have to be inserted into the Fox-Flory relationship \documentclass{article}\pagestyle{empty}\begin{document}$ {{\left[ \eta \right] = \Phi (\overline {r_{{\rm av}}^{\rm 2} } )^{{3 \mathord{\left/ {\vphantom {3 2}} \right. \kern-\nulldelimiterspace} 2}} } \mathord{\left/ {\vphantom {{\left[ \eta \right] = \Phi (\overline {r_{{\rm av}}^{\rm 2} } )^{{3 \mathord{\left/ {\vphantom {3 2}} \right. \kern-\nulldelimiterspace} 2}} } {M_{{\rm av}} }}} \right. \kern-\nulldelimiterspace} {M_{{\rm av}} }} $\end{document} if the number-, weight-, or z-average dimensions are to be determined for polymolecular polymer samples. The resulting complex molecular weight averages \documentclass{article}\pagestyle{empty}\begin{document}$ M_{r_{\rm n} } \eta _{\rm w},{\rm }M_{r_{\rm w} } \eta _{\rm w} $\end{document}, and \documentclass{article}\pagestyle{empty}\begin{document}$ M_{r_{\rm z} } \eta _{\rm w} $\en{document} are compared with simple molecular weight averages and for Schulz-Zimm and logarithmic normal distributions of the molecular weight their numerical relations to the viscosity-(Mη), number- (Mn), and weight-average molecular weight (Mw) calculated. A simple straight-forward method is outlined for the determination of the number-, weight-, and z-average dimensions of polymolecular polymers from viscosity and gel permeation chromatography measurements.
    Additional Material: 3 Ill.
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    Interaction of sodium dodecyl sulfate with poly(L-lysine) in aqueous solution (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1819-1827 
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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 interactions between a homopolypeptide, poly(L-lysine) [(Lys)n], and an anionic surfactant, sodium dodecyl sulfate (NaDodSO4), were studied by 13C NMR spectroscopy in D2O solution. By observing the chemical shift of the ε-amino carbon of lysine monomer in D2O solution at pH 7,3 in presence and absence of NaDodSO4, direct evidence was found for electrostatic interaction between the protonated lysine ε-amino group and the head group of the anionic surfactant. At this pH, the (Lys)n chain in NaDodSO4 solution adopts the β-form conformation and the solubility of NaDodSO4/(Lys)n complexes is too small to observe 13C-spectra. At more alkaline solutions, where the (Lys)n chain forms α-helices, the surfactant's polar group interacts with the uncharged lysyl side chain through hydrogen bonding. In the initial binding of the surfactant to (Lys)n, both the surfactant head group and alkyl chain contribute to the association with (Lys)n. With an excess of surfactant bound to α-helical (Lys)n, NaDodSO4/(Lys)n complexes show high solubility and all carbon atoms of the surfactant molecules show micelle shifts. These results suggest that the surfactant molecules form micellelike clusters around the (Lys)n helices exposing the surfactant polar head group to the medium and enhancing the solubility of NaDodSO4/(Lys)n complexes.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820621
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    The relation between phase transition and crystallization behavior of 1,4-trans-poly(butadiene)Herrn Prof. Seefelder zum 60. Geburtstag gewidmet (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1859-1874 
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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 crystallization behaviour of pure 1,4-trans-poly(butadiene) (1,4-PTBD) from dilute solutions in heptane and its relation to the phase transition phenomena in the solid state is investigated. Depending on whether the nucleation occurs in the high-temperature modification II or the low-temperature modification I two different regimes of crystallization behaviour are observed which in turn determine the crystal thickness as well as the phase transition and annealing behaviour of the crystals. The equilibrium phase transition temperature (I-II) is 356 K, the corresponding enthalpy is 144 J.g-1; the equilibrium melting temperature is 437 K and the enthalpy of melting is 69 J.g-1. The surface free energy terms are obtained relating the crystal thicknesses measured by SAXS and DSC to the temperatures of phase transition and melting, resp. Following Hoffman's theory of nucleation and growth the theoretical curves for the rate of nucleation and crystal growth are calculated and compared to the experimental results.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820626
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    Preparation and homopolymerization of 2-arylazo-5-dimethylaminobenzyl acrylates and methacrylates (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1929-1935 
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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: 2-Arylazo-5-dimethylaminobenzyl alcohols (1) were prepared and used for the preparation of 2-arylazo-5-dimethylaminobenzyl acrylates (2) and methacrylates (3); these compounds were characterized by melting points, IR and 1H NMR spectra. The coloured compounds 2 and 3 were subjected to radical homopolymerization in solution initiated with AIBN at 70°C, and [η], IR and 1H NMR spectra of the polymers were determined. Alternatively, the coloured polymer with 2-(2-chlorophenylazo)-5-dimethylaminobenzyl methacrylate monomeric units was prepared by coupling of the copolymer of 3-dimethylaminobenzyl methacrylate and styrene with 1-chlorobenzenediazonium chloride.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820705
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