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  • Articles  (1,545)
  • Chemistry  (1,545)
  • Analytical Chemistry and Spectroscopy  (164)
  • 2005-2009
  • 1980-1984  (1,545)
  • 1925-1929
  • 1983  (1,545)
  • Physics  (1,545)
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  • Articles  (1,545)
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  • 2005-2009
  • 1980-1984  (1,545)
  • 1925-1929
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  • 1
    Electronic Resource
    Electronic Resource
    Biomimetic approach to the design of a pyridoxal enzyme model, 3Part 2: cf.1. Synthesis of 4-formyl-3-hydroxy-5-methacryloylaminomethyl-2-methylpyridine and its 5′-N-methylated analogue (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1-7 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The synthesis of 4-formyl-3-hydroxy-5-methacryloylaminomethyl-2-methylpyridine (7a) and 4-formyl-3-hydroxy-5-(N-methacryloyl-N-methyl)aminomethyl-2-methylpyridine (7b) is reported. The intermediate products 5-aminomethyl-2,2,8-trimethyl-2H,4H-[1,3]-dioxino[4,5-c]-pyridine hydrochloride (3a), 2,2,8-trimethyl-5-methylaminomethyl-2H,4H-[1,3]-dioxino[4,5-c]-pyridine hydrochloride (3b), 5-methacryloylaminomethyl-2,2,8-trimethyl-2H,4H-[1,3]-dioxino-[4,5-c]pyridine hydrochloride (5a), 5-(N-methacryloyl-N-methyl)aminomethyl-2,2,8-trimethyl-2H,4H-[1,3]-dioxino-[4,5-c]pyridine hydrochloride (5b), 3-hydroxy-4-hydroxymethyl-5-metha-cryloylaminomethyl-2-methylpyridine (6a) and 3-hydroxy-4-hydroxymethyl-5-(N-methacryloyl-N-methyl)aminomethyl-2-methylpyridine (6b) were isolated and identified.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021840101
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  • 2
    Electronic Resource
    Electronic Resource
    Polymerization of lactams, 53Part 52: cf.1. Anionic polymerization of 2-pyrrolidone accelerated with CO2, part 2 (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 41-57 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The anionic polymerization of 2-pyrrolidone (3) initiated with its potassium salt (1) (2-oxo-1-pyrrolidinylpotassium) and carbon dioxide was studied under optimal conditions. On the basis of a detailed experimental analysis, it is suggested to consider the investigated polymerization in the presence of gaseous CO2 as an accelerated non-activated polymerization. Alkali 2-oxo-1-pyrrolidine carboxylate, which is formed in the system by reaction of CO2 with 1, probably does not take part directly in the polymerization process and excerts only a controlling role.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021840105
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  • 3
    Electronic Resource
    Electronic Resource
    Preparation of 5-hydroxy-7-methoxy-2,2-dimethyl-6-octyl(and 8-octyl)-4-chromanones and their Properties as UV Absorbers (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 71-76 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 5-Hydroxy-7-methoxy-2,2-dimethyl-6-octyl(and 8-octyl)-4-chromanones (2a and 2b) were synthesized via 5,7 dihydroxy-2,2-dimethyl-6-octyl (and 8-octyl)-4-chromanones (1a and 1b) from phloroglucinol as a starting material. Cyclohexane solutions of 1a, 1b, 2a, and 2b were irradiated. The photostability of 2a and 2b was found to be better than that of 1a and 1b. Poly(vinyl chloride) film containing 6, 7 wt.-% of 2b was found to be most stable against photooxidation.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021840108
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  • 4
    Electronic Resource
    Electronic Resource
    OH Radical-induced chemical reactions of polynucleotide complexes (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 165-173 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(A + U), the 1:1 complex of poly(riboadenylic acid), poly A, and poly(ribouridylic acid), poly U, at pH 8 and self-complexed poly A at pH 4 exist as double helices in dilute aqueous solution. These complexes exhibit a similar behavior as native calf thymus DNA upon irradiation with 16 MeV electron pulses. Thus time resolved Rayleight light scattering measurements showed that crosslinking and double strand breakage can be clearly separated, the former proceeding faster than the latter. The extent to which the two processes occur depends on the ionic strength of the solution. At ionic strenghts exceeding 10 -1 mol/l crosslinking is the dominant process indicating that hcrit, the critical length between two single strand breaks for the accomplishment of double strand breaks, is strongly reduced. The investigation of complexes of poly A and Mg2+ ions revealed that the destruction of salt bridges is the rate determining process for the decrease of the light scattering intensity due to mainchain scission. This implies that life-times of salt bridges can be determined.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021840117
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  • 5
    Electronic Resource
    Electronic Resource
    The chemically initiated high pressure polymerization of ethylene (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 193-206 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the high-pressure ethylene polymerization initiated by di-tert-butyl peroxide were measured via quantitative near-infrared spectroscopy at temperatures between 130°C and 165°C to a maximum pressure of 3 kbar. The overall polymerization rate was found to be first order in ethylene concentration and of the order 0,5 in peroxide concentration. The overall activation energy and the overall activation volume were determined to be E0 = 107,2 ± 7,5 kJ · mol-1 and Δ V0≠ = - 17,5 ± 5,0 cm3 · mol-1, respectively. From the overall quantities and from the decomposition rate of di-tert-butyl peroxide determined in independent spectroscopic high-pressure high-temperature experiments, kp · kt-1/2 (kp and kt are the propagation and termination rate constants, respectively) and the corresponding activation parameters, Ep - 1/2 Et and Δ vp≠ - 1/2 Δvt≠, were derived for the high-pressure ethylene polymerization. These data enable the overall polymerization rate to be determined also for high-pressure ethylene polymerizations initiated in any different way, provided the initiation rate law is known. The procedure is illustrated for the ethylene polymerization initiated by tert-butyl peroxypivalate.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021840119
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  • 6
    Electronic Resource
    Electronic Resource
    Interaction between dyes and polyelectrolytes, 14Part 13: M. Shirai, M. Ohyabu, Y. Ono, M. Tanaka, J. Polym. Sci., Polym. Chem. Ed. 20, 555 (1982). Triplet energy transfer in a cationic dye-polyanion system (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 153-163 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymers with different fractions of azobenzene residues were prepared by radical copolymerization of methacrylic acid with 4′-phenylazomethacrylanilid. The triplet excitation energy transfer from methylene blue (1) to the azobenzene residues in the polymers was investigated by using the 1-photosensitized cis → trans isomerization of the azobenzene residue. The efficiency of the triplet excitation energy transfer from 1 to 4-(4′-phenylazoanilinocarbonyl)butanoic acid (4) as a monomer model compound. The number of azobenzene residues per polymer molecule and the molecular weight of the polymer were important factors for the efficient triplet excitation energy transfer. On addition of NaCl the energy transfer efficiency was lowered, suggesting that the binding of 1 to the polymer by electrostatic forces plays an important role. Binding of 1 to the polymers was investigated spectrophotometrically. Correlation with the binding of 1 to the polymers and the efficiency of triplet excitation energy transfer between 1 and azobenzene residues in the polymers is discussed.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021840116
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  • 7
    Electronic Resource
    Electronic Resource
    Untersuchung der teilschritte der ethylen-hochdruck-polymerisation, 1. Druckabhängigkeit der einzelnen geschwindigkeitskonstanten (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 207-216 
    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 calculate the average molecular weight, the molecular weight distribution or the branching of low density polyethylene, the individual values of the rate constants of the different reactions involved in the free radical polymerization are required. The method of rotating sector was applied to determine the rate constants of chain propagation and chain termination in a wide range of temperatures and pressures. This first part of the work reports the influence of the pressure. It was found that the rate constant kp of the chain propagation increases with rising pressure whereas the rate constant kt of chain termination decreases. The effect of the pressure on kp can be explained in terms of the activation volume. The decrease of kt with pressure is caused by a diffusion controlled termination reaction.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021840120
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  • 8
    Electronic Resource
    Electronic Resource
    On the mechanism of the flow process of poly(ethylene terephthalate) (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 217-223 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanism of “flow process” defined as drawing by which neither crystallization nor molecular orientation takes place was clarified on the basis of its direct experimental evidences on drawing of “amorphous” poly(ethylene terephthalate) films. In a certain temperature range above Tg, the polymer molecules are deformed and oriented on drawing, “inter-molecular secondary linkage” playing an important role in the transmission of the applied force. When this intermolecular linkage breaks down above a certain critical temperature, the polymer molecules may slip past each other and flow independently, resulting in a large deformation without inducing any molecular orientation and crystallization. At higher temperatures crystallization occurs inducing the orientation as well.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021840121
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  • 9
    Electronic Resource
    Electronic Resource
    Synthèse de polysiloxanes organofonctionnels, 1. Chloration des poly(diméthylsiloxane)s par le chlorure de sulfuryle (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 263-276 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sulfuryl chloride was used as chlorination agent of poly(dimethylsiloxane)s (1) in order to obtain poly(dimethylsiloxane-co-chloromethylmethylsiloxane) and it was found to be more specific than molecular chlorine. Identification of chlorinated and chlorosulfonated units was shown to be possible by comparison of the results of 1H NMR spectroscopy with those obtained by GLC analysis of the mixtures obtained from octamethylcyclotetrasiloxane (2). After having shown that the distribution of the various types of methyl groups in 1 and 2, modified in this way, fits correctly a binomial law and that chlorosulfonated units can be hydrolysed, copolymers containing 20 to 25% of chloromethylated units and less than 2% of unwanted dichloromethylated units are accessible by use of this chlorination agent.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021840203
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  • 10
    Electronic Resource
    Electronic Resource
    Liquid crystalline main chain polymers with highly flexible siloxane spacers (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 253-262 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The synthesis and the phase behaviour of liquid crystalline main chain polymers are described. In these poly- and copolyesters the mesogenic units are linked by highly flexible oligodimethylsiloxane spacers. The comparison of their phase behaviour with that of polyesters known from the literature shows that dimethylsiloxane spacers as a replacement for alkyl spacers are leading to a drastic decrease of the transition temperatures. Depending on the length of the spacer glass transitions as low as -111°C can be achieved. The widths of the liquid crystalline phases thereby are retained up to a spacerlength of 13 oxydimethylsilanediyl (dimethylsiloxane) units. The homopolyesters mainly show smectic phases. In contrast to this nematic phases are found for copolyesters in which either the spacerlength or the mesogenic unit was varied. In one case a nematic phase was found over a temperature range of 311°C.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021840202
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  • 11
    Electronic Resource
    Electronic Resource
    On the molecular weight determination by vapour pressure osmometry, 4Part 3: R. V. Figini, M. Marx-Figini, Makromol. Chem. 182, 437 (1981).. Experimental proof of the deviation of MVPO from Mn (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 319-322 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kind of molecular weight average MVPO resulting from vapour pressure osmometry (VPO) measurements on solutions of paucimolecular polymer mixtures of different compositions is studied with a Hewlett Packard Model 302 B. Recent theoretical calculations which predicted that MVPO 〉 Mn are confirmed. The experimentally found quotient MVPOMn is between 1,04 and 1,26, being the greater, the greater is the polydispersity of the mixture, which is agreement with the former mathematical derivations.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021840208
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  • 12
    Electronic Resource
    Electronic Resource
    Study of step-growth polymerizations using epoxy-carboxy reaction, 1. Study of the epoxy-carboxy reaction on models in solvents of low or medium dielectric constants (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 323-334 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Due to its importance in the field of block-polycondensation and of chemical modification, we carried out an extensive study of the epoxy-carboxy reaction on models. This papier is related to the reaction of benzoic acid with 1-phenoxy-2,3-epoxypropane in the presence of a basic catalyst, N,N-dimethyldodecylamine. It is carried out in low polar solvents (xylene, chlorobenzene, and o-dichlorobenzene); essential kinetic parameters are reported. From studies carried out under stoichiometric or non-stoichiometric conditions a general rate equation (υ = k [acid]0.5 [epoxy] [amine]) is obtained. Kinetic relations are the same, no matter what the catalyst is: dimethyldodecylammonium benzoate or free amine. From these kinetic data it results that the overall mechanism involves two steps.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021840209
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  • 13
    Electronic Resource
    Electronic Resource
    Polymer conformation and NMR chemical shifts, 7Part 6: cf. 10.. Conformational analysis of random copolymers (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 371-381 
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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 method is developed for the conformational analysis of copolymers with randomly distributed stereo- and comonomer-sequences. The conformational probabilities of dyad sequences constituting a random copolymer chain are calculated as a function of the copolymer composition which is derived from the monomer reactivity ratios and the comonomer feed ratio. The applicability of this method is verified in the conformational analyses of poly(methyl acrylate-co-styrene) and poly(methyl methacrylate-co-styrene). The calculation indicates that the conformational stabilities of dyad sequences are scarcely dependent on the copolymer composition in the former copolymer, whereas they are susceptible to the composition in the latter copolymer. This conformational behavior apparently reflects the geometrical difference between the copolymers: the former is composed of two mono-substituted monomers and the latter of sterically nonequivalent monomers, viz. mono- and di-substituted vinyl compounds. The composition-dependences of 13C NMR chemical shifts of these copolymers are interpreted, based on the conformational calculation by this method.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021840213
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  • 14
    Electronic Resource
    Electronic Resource
    Etude des prépolymères époxydes par chromatographie et 1H NMR à 350 MHz (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 411-429 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The epoxy resins (DGEBA) obtained from 4,4′-isopropylidendiphenol (bisphenol A) and 1-chloro-2,3-epoxypropane (epichlorohydrin) and synthetized by the “taffy” process were found to consist of oligomers. The composition of prepolymers could be deduced from gel permeation chromatography (GPC), and particularly by high pressure liquid chromatography (HPLC). In the more resolved HPLC spectrum each oligomer was found to be accompanied by satellite peaks. The functionality of the prepolymers, determined by 1H NMR spectroscopy and cryometric or vapour pressure osmometric measurements was found to be less than two. These phenomena are due to the existence of abnormal chain ends having no epoxy group. The structure of the main components spearated by preparative GPC was studied by 1H NMR. For the impurities, the two indentified structures of chain ends are primary and secondary alcohol functions. Finally the compositions of three DGEBA were determined.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021840216
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  • 15
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    Electronic Resource
    Glass transition and melting temperatures of random copolyesters of poly(ethylene terephthalate) with p-hydroxybenzoic acid, 3Part 2, cf.: M. Balachandar, T. Balakrishanan, H. Kothandaraman, J. Polym. Sci., Polym. Chem. Ed. 20, 2621 (1982). (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 443-453 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The glass transition temperature of the random copolyesters of poly(ethylene terephthalate) and p-hydroxybenzoic acid prepared by molten state polycondensation increases with increasing concentration of p-oxybenzoate units (oxy-1,4-phenylenecarbonyl units). The observed values of the glass transition temperature are compared with the values predicted from various empirical equations on the Tg's of copolymers and the concave Tg composition curve is explained in terms of the internal stiffening effect of the p-oxybenzoate unit. The melting temperatures of the copolyesters vary with composition and show an eutectic phase diagram. The melting temperature and enthalpy of fusion of the homopolymer of p-hydroxybenzoic acid were determined making use of Flory's equation on the melting point of a copolymer.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021840218
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  • 16
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    Electronic Resource
    Untersuchung der teilschritte der ethylen-hochdruckpolymerisation, 2Teil 1: cf.1.. Druck- und temperaturabhängigkeit der einzelnen geschwindigkeitskonstanten (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 849-859 
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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 the first part of this series the individual rate constants of the radical polymerization of ethylene are reported in dependency of pressure at 405 K. By further measurements under 500 - 1750 bar and 400 - 470 K, using again the method of the rotating sector, the dependency of the rate constants on both pressure and temperature was determined. With increasing temperature the rate constant of chain growth kp as well as that of chain termination kt increases. With increasing pressure, kp increases, whereas kt decreases because of the diffusion controlled termination reaction. For the chain growth an activation energy of Ep = 37 kJ/mol and an activiation volume of Δvp≠ = -25,5 ml/mol was found. The activiation parameters of the chain termination are Et = 9,9 kJ/mol and Δvt≠ = 7 ml/mol. Based on these results and literature data the rate constants of different chain transfer reactions involved in the high pressure polymerization of ethylene and their dependency on temperature and pressure were evaluated.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021840419
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  • 17
    Electronic Resource
    Electronic Resource
    Functional metal-porphyrazine derivatives and their polymers, 7Part 6: cf.8.. Synthesis and properties of metal-2,9,16,23-tetracarboxyphthalocyanine covalently bound to poly(2- or 4-vinylpyridine-co-styrene) (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 691-699 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Metal-2,9,16,23-tetracarboxyphthalocyanines(Mt-taPc's) [Mt = Fe(III), Co(II), Ni(II), Cu(II)] covalently bound to poly(2- or 4-vinylpyridine-co-styrene) were synthesized by Friedel-Crafts reaction of the styrene units of the copolymers with Mt-taPc tetraacid chloride. The copolymers contain about 0,3 to 14,6 mol-% Mt-Pc rings and are soluble in methanol, ethanol, and N,N-dimethylformamide. The coordination spheres around the Mt-Pc rings were characterized by electronic as well as ESR spectra and by viscosity measurements. The dimerization of Mt-taPc in the copolymers is sterically hindered by the polymer chain. The copolymer supported Fe(III)- or Co(II)-taPc's are of the five coordinate high spin type in DMF solution. One coordination site at axial position of the Mt-Pc ring may be occupied by an N atom of a pyridine group. The electronic structures of the metal atoms may be useful in catalytic reactions.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021840403
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  • 18
    Electronic Resource
    Electronic Resource
    Syntheses and characterization of polycondensation products derived from β-(4-methoxy-3-methyl)phenylglutaconic acid and diols (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 733-735 
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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: Five new copolyesters 3a - e were prepared by reacting β-(4-methoxy-3 methyl)phenylglutaconic acid dichloride (1 b) with diols 2 a - e. The polymers were characterized by IR and TG. All polymers were found to decompose in the range of ≈200 to ≈650°C.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/macp.1983.021840407
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  • 19
    Electronic Resource
    Electronic Resource
    Reactive microgels by the self-emulsifying copolymerization of unsaturated polyester resins with acrylic and methacrylic esters (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 755-762 
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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 self-emulsifying copolymerization of unsaturated polyesters (UP) with various acrylic and methacrylic esters was studied. The structure of comonomers significantly influences the character of microgels obtained. Among these monomers the copolymerization of UP with methyl methacrylate (MMA) was investigated in detail in order to make clear the behavior of this polymerization as compared with that of styrene. The water/monomer and UP/MMA ratios were found to be the most important factors controlling the molecular weight and solution viscosity of the microgels. The relationship between M̄w and intrinsic viscosity of microgels suggests that the microgels from MMA have less compact structure than those from styrene.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1983.021840410
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  • 20
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    Electronic Resource
    Pharmacologically active polymers, 23Part 22, cf.: T. Hirano, H. Ringsdorf, D. S. Zaharko, Cancer Res. 40, 2263 (1980).. Linear and branched zwitterionic derivatives of polyethyleneimine as carriers for pharmacologically active components (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 793-801 
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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: To obtain a carrier polymer for pharmacologically active components, linear polyethyleneimine (LPEI) was chemically modified by reactions with acrylic acid (1a), acrylamide (1b), acrylic acid esters (1c and 1d), sodium chloroacetate, and hydrochloric acid. All product polymers 2a - 2e are soluble in water. Among these, 2a and 2e, β- and α-amino acid derivatives, respectively, show no acute toxicity in mice up to dosages of 1 g/kg i. v. Similar types of polymers 5a and 5b and a polymer containing phosphonic acid moieties (5d) derived from branched polyethyleneimine (BPEI) were prepared. 5a and 5b are also nontoxic regardless of the molecular weight of four kinds of BPEI and of the wide range of carboxylic group content in the polymer. It is suggested that the zwitterion form contributes to the nontoxic nature of β-and α-amino acid type polymers. The present results show that amino acid type polymers derived from LPEI and BPEI can be used as carrier polymers for pharmacologically active components.
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    Promotion of charge-transfer complex formation by β- or γ-cyclodextrin (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 837-847 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The formation of charge-transfer (CT) complexes between eleven naphthalene derivatives and eight di- or trinitrobenzene derivatives in water and in water-organic solvent systems has been studied in the presence and absence of β- or γ-cyclodextrin (β- or γ-CDx), respectively. Data of UV absorption and circular dichroism (CD) clearly revealed that γ-CDx, in several cases, assists CT complex formation by accommodating both electron donor (D) and acceptor (A) molecules in its cavity simultaneously. Thus the weak CT band was intensified and even some systems in which CT complex formation was usually not observed produced CT complexes by the addition of γ-CDx. In contrast, β-CDx did not promote markedly the CT complex formation except in one case. It did promote the CT complex formation between α-naphthylacetic acid (α-NAA) and picric acid (PA), manifesting the capability of β-CDx to include two aromatic molecules. Magnetic circular dichroism (MCD) associated with the CT bands was detected for a π - π* type CT complex for the first time, but its intensity was quite weak as anticipated from theory.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1983.021840418
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  • 22
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    Asymmetric selective oligomerization of chloromethyloxirane (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 895-906 
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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: Chloromethyloxirane (CMO) undergoes an asymmetric selective oligomerization with a binary catalyst system comprised of triethylaluminium and an optically active cobalt complex, N,N'-disalicylidene-(1 R)-1,2-cyclohexanediyldiaminatocobalt(II). A series of optically active oligomers obtained were isolated and characterized. Two kinds of linear oligomers were produced with respect to the end groups, namely epoxy- and halohydrin-ended oligomers. A mechanism for the selective formation of linear oligomers by the present catalyst system is proposed.
    Additional Material: 7 Ill.
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  • 23
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    Electron transfer process in the microdomains of poly(sodium styrenesulfonate)-poly(alkylene viologen) complexes (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1061-1070 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The electron transfer process in the microdomain of a polyion complex composed of poly(sodium styrenesulfonate), (syst. name: poly[sodium 1-(4-sulfonatophenyl)ethylene]), and poly(alkylene viologen)s 1 with 3 to 10 methylene groups between two adjacent viologen units was analyzed by means of voltammetry with a rotating disc electrode. Although the stability of 1 on the graphite electrode was improved by the formation of a polyion complex with poly(sodium styrenesulfonate), a smaller surface charge was observed in the polyion complex as compared with the electrode coated with poly(alkylene viologen) alone. Since the migration of the counter ion was clarified to be indispensable for the electron transfer in this case, the microdomain of polyion complexes should be formed by tightly-shrunk polyelectrolyte chains. Furthermore, the electron transfer in the microdomain of the polyion complex is hardly detected, when the electrode is coated with an excess of the complex. The electron transfer strongly depended on the average distance between two adjacent redox sites in the matrix. These matrixes were suggested to be controlled by the subtle balance of hydrophobicity and charge density of 1.
    Additional Material: 7 Ill.
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  • 24
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    New experiments concerning the mechanism of solid-state photopolymerization of 2,5-distyrylpyrazineDedicated to Prof. Dr. H.-J. Cantow on the occasion of his 60th birthday, with warmest personal wishes (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1103-1119 
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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 photoinduced formation of oligomers in single crystals of 2,5-distyrylpyrazine (DSP) was investigated by X-ray and electron diffraction techniques and also by gel permeation chromatography (GPC). The DSP crystals were characterized for the presence and nature of dislocations by dark-field images and etch-pit studies. Small angle grain boundaries were identified to be the prominent feature, but in general the crystals were highly perfect. A correlation between the sites of the defects and the formation of the photoproduct could not be detected. The oligomers formed in a solid-solution under appropriate irradiation conditions. Thus, DSP oligomer of number average degree of polymerization P̄n = 3,2 in macroscopic single crystal texture was obtained for the first time using a laser light source at 478 nm. Deterioration of the single crystal texture of DSP usually observed during photopolymerization is explained as being caused by inhomogeneous light distribution which in turn causes an inhomogeneous product distribution with accumulation of large strain fields. These can be made visible by the multiplication of etch pits. Phase separation between oligomer and polymer is observed on further irradiation of the oligomer single crystals. The oligomer phase seems to play the role of an intermediate in the photopolymerization of DSP at wavelengths λ 〈 400 nm. The molecular weight distribution of the oligomers was studied by GPC. The data are only compatible with the assumption that the rate constant of dimerization is higher than that for the addition of a monomer to an already existing oligomer.
    Additional Material: 13 Ill.
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    Functional monomers and polymers, 105Part 104: Y. Sakuma, Y. Inaki, K. Takemoto, J. Polym. Sci., Polym. Chem. Ed., in press.. Synthesis of poly(β-alanine) from a new type of active amino acid ester (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1171-1178 
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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: Active β-alanine esters having dipeptide groups, which are capable of forming hydrogen bonds between the side chains, were prepared in the form of hydrogen chloride salts. The polycondensation of these salts was studied in non-polar solvents, in the presence of triethylamine. In the case of the ester with β-alanyl-β-alanine as dipeptide moiety, the polycondensation proceeded smoothly in chloroform solution. To explain the characteristic feature of the polycondensation, an ordered aggregation of the ester molecules is assumed to play an important role. The ester with glycylglycine as dipeptide moiety, however, did not undergo a polycondensation.
    Additional Material: 7 Ill.
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  • 26
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    Conformational analysis of polyoxyethylene using empirical force field methods (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1285-1293 
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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: Conformanational energies of various oligo (oxyethylene) isomers were calculated by the empirical force field method, and statistical mechanics calculations of the chain dimensions and the dipole moments were carried out. The results are seriously different from those obtained for poly (oxymethylene). Although the first-order steric interactions in POE are of the same order of magnitude as those in n-alkane chains, the second-order interactions are significantly different. The second-order interactions arising from rotations around two consecutive bonds of OCH2CH2OCH2 in g± g∓ conformation have greatly reduced steric repulsions. It was found that the reduced second-order interaction plays an important role in the configurationdependent properties of POE. The agreement of the calculated values for the unperturbed dimensions and the temperature coefficients obtained from the force field method with experimentally observed ones is fairly good.
    Additional Material: 1 Ill.
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    Role of cocatalysts in polymerizations initiated with benzyl derivatives of transition metals, 1. Polymerization of ethylene (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1389-1395 
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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: Polymerization of ethylene initiated in naphta solution by Zr(CH2C6H5)4 at 200°C under high purity conditions showed a cocatalytic effect of water with a maximum rate for a mole ratio H2O/Zr close to 0,1. No activity was observed for the hypothetical compound (C6H5CH2)3ZrOZr(CH2C6H5)3. Ethylene polymerization was also initiated with supported catalysts obtained by reaction of Zr(CH2C6H5)4 with silicium oxide or pre-dried aluminium oxide with an increase of activity (by a factor of 5). The resulting polyethylenes were found to be virtually linear with 1,5 CH3 groups for 1000 C atoms and with melting points of 134 - 136,5°C. They have high molecular weights with very broad distribution. These results were interpreted by a mechanism involving Ziegler-like active centers.
    Additional Material: 2 Ill.
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    Chemische synthese verzweigter polysaccharide, 109. Mitteilung: cf.6.. Polymere mit amidartig gebundenen mono- und oligosaccharid-seitenkettenHerrn Professor Dr. H.-J. Cantow zum 60. Geburtstag gewidmet (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1441-1458 
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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: Binding of mono-, di-, and oligosaccharides by amide linkage to polymers carrying carboxylic or amino groups was studied with synthetic polymers (poly(acrylic acid), poly(vinylamine)) and polysaccharide derivatives (e.g. chitosan). Suitable methods are described which allow a variation of the number and lenght of the attached saccharide branches. In the absence of salt, all products with a degree of substitution (DS) 〈 1 show polyelectrolyte behaviour. Compared with the unsubstituted polyelectrolytes, for the branched polymers a substantial increase of the viscosity was observed within a certain range of branch density. In the case of glucose side chains, the maximum viscosity was found near DS = 0,1. In the case of maltose side chains, this maximum of the viscosity occurred at higher DS. A similar but smaller increase in the viscosity was observed in 0,1 M NaCl solution. The results are explained by a shielding of the backbone charges from the counterions and by an additional chain stiffening effect resulting from hydrogen bonds, i.e., ring formation between the amide linkage and adjacent free carboxylic or amino groups.
    Additional Material: 3 Ill.
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    Properties of liquid crystalline polymers in solution, 1. Determination of the molecular weight of polymethacrylates with mesogenic sidegroupsDedicated to Professor Dr. H.-J. Cantow on his 60th birthday (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1489-1496 
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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: Derivatives of poly(methacrylic acid) with mesogenic sidegroups are aggregated in solution. Through structural changes which also take place in the solid state, the fraction of the aggregates increases with storage time. The formation of aggregates depends on temperature and occurs relatively slowly. In solution, the degree of aggregation strongly depends on the solvent. This aggregation leads to relatively high tacticity in products obtained by radical initiated polymerisations.
    Additional Material: 6 Ill.
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    Orientierungsverhalten von segmentierten polyetherurethanen in abhängigkeit von der dehnung und den verwendeten lösungsmittelnHerrn Prof. Dr. Cantow zum 60. Geburtstag gewidmet (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1529-1546 
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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 solvent influence on two- phase structures resulting from drying films of segmented polyetherurethanes of different hard segment contents and molecular weights was investigated by infrared dichroism measurements of the orientational behaviour of the hard segments. A low density of physical crosslinking and/or minor association in solution leads to a lamellae structure resulting in an inhomogeneous distribution of stress at elongation. The formation of lamellae is impeded, if the solution shows pronounced formation of associates. Destruction of the lamellae can be monitored by studying the orientational behaviour for repeated deformations and by means of orientation-extension-hysteresis experiments. Stress-strain diagrams exhibit no contradictions to the discussed structural transformations by the influence of different solvents.
    Additional Material: 15 Ill.
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    High conversion copolymerization, 2Part 1: cf.8.. Styrene/maleic anhydride copolymer composition studies (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1597-1602 
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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 free radical initiated copolymerization of styrene with maleic anhydride at high conversions is studied. The data of the fractional conversion of the comonomers, of the fractional copolymerization rate, of the instantaneous and cumulative composition of the copolymer for the copolymerization of an equimolar mixture of styrene and maleic anhydride in ethyl methyl ketone (at 60°C) and in 1,4-dioxane (at 120°C) up to high conversions as a function of the reaction time (resp. conversion) are presented. Negligible differences at 60°C, but significant ones at 120°C were found between the experimentally measured fractional compositions and those calculated according to the integrated form of the copolymer composition equation (Mayo-Lewis equation), using the published values for the copolymerization reactivity ratios.
    Additional Material: 3 Ill.
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    A correlation of anodic peak potentials with HOMO energies of various monomers (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1661-1667 
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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: Electroinitiated cationic polymerization of olefins can be initiated by direct electron transfer from the highest occupied molecular orbital (HOMO) of monomers, by constant potential electrolysis. Potentials, at which some monomers lose electrons, were measured by cyclic voltammetry. Measurements were made on a Pt electrode versus Ag0/Ag+, in acetonitrile. The measured anodic peak potentials (Ep,a) were correlated to HOMO energies (∊m), calculated by Hückel molecular orbital (HMO) considerations for coplanar molecules. For methyl-substituted monomers the ω-technique was also applied. A linear equation has been developed for Ep,a as a function of ∊m, for styrene derivatives having +I and +E substituents.
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    Lyotropic and thermotropic liquid-crystalline phase formation from fractions of a semiflexible cellulosic polymer (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1727-1740 
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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 benzoic acid ester of (2-hydroxypropyl)cellulose (BzPC) was prepared and fractionated from acetone solution by precipitation with methanol-water (85:15, by volume). The fractions were characterized by low-angle laser light scattering in tetrahydrofuran, and by size exclusion chromatography with a low-angle laser light scattering detector. Dilute solution viscosities were measured in acetone and benzene, and the results were interpreted on the basis of a worm-like chain model for BzPC. The critical concentrations of polymer necessary to form lyotropic cholesteric phases in acetone and benzene were found to decrease as the molar mass of the polymer increased, reaching a limiting volume fraction of ≈ 0,35 for high molar mass fractions. The experimental results were compared with the prediction of recent theories for the formation of liquid crystalline phases from semiflexible polymers; the chain parameters required by the theories were estimated from dilute solution viscosities. The fractions of BzPC also showed a thermotropic transition from liquid crystalline phase to isotropic melt. The transition temperature increased sharply with increasing molar mass to reach a limiting value of 176°C.
    Additional Material: 7 Ill.
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    Functional monomers and polymers, 109Part 108: Y. Suda, Y. Inaki, K. Takemoto, J. Polym. Sci., Polym. Chem. Ed., in press.. Asymmetric inclusion polymerization of (E)- and (Z)-2-methyl-1,3-pentadiene in apocholic acid canalsDedicated to Professor H. J. Cantow on the occasion of his 60th birthday (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1771-1779 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Asymmetric inclusion polymerization of the prochiral monomers (E)- and (Z)-2-methyl-1,3-pentadiene (3a and 3b), in apocholic acid (2) canals was performed under various conditions to find out the factors controlling the asymmetric induction during the polymerization. Ozonolysis of the resulting polymers and subsequent transformation of the resulting 2-methyl-4-oxovaleric acid (4) into its 2,4-dinitrophenylhydrazone revealed the predominant formation of the (R)-absolute configuration. The optical yield was high in the initial stage of the polymerization and decreased gradually as the polymerization proceeds. To obtain a high optical yield the polymerization was performed at low temperature applying a 1:1 mole ratio monomer/apocholic acid, and an irradiation dose 〈 1 Mrad. The optical yield amounted to 36% at maximum, which is the highest value obtained so far in the asymmetric polymerization of 1,3-pentadiene derivatives using canal complexes or other known methods.
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    29Si NMR-untersuchungen an polykieselsäureestern (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1817-1822 
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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: Linear and branched siloxanes were prepared by partial hydrolysis of silicon tetrachloride and by esterification of the products of hydrolysation with methyl and ethyl nitrite. 29Si NMR spectra made it possible to distinguish between the isomers of each oligomer up to the heptamer. Linear relationships between the 29Si chemical shifts of the ethyl and the methyl esters on one hand and between the ethyl esters and the poly(silicic acid)s on the other hand were observed. However, due to the different effect of neighboring building units, there are only poor relationships between the 29Si data of the esters and the chloro derivatives.
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    Radical polymerization of methyl methacrylate initiated by the liquid crystalline compound cholesteryl oleyl carbonate (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1555-1560 
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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: Polymerization of methyl methacrylate (MMA) and vinyl acetate (VAc) at 30, 55, 65, 75, and 85°C in the presence of the cholesteryl liquid crystal compound cholesteryl oleyl carbonate (CHOC) are reported. The conversion increases, whereas the molecular weight remains constant, with increase in concentration of CHOC in the range 0,2 to 0,6 mol-%. The activation energy for the polymerization of MMA was found to be 66,3 kJ/mol. The polymerization is inhibited in the presence of the radical scavengers 1,1-diphenyl-2-picrylhydrazyl (DPPH) and hydroquinone. VAc does not polymerize in the presence of CHOC for 20 h at 65°C. The interaction between MMA and CHOC is investigated by viscometry of toluene solutions and by UV spectrophotometry of CCl4 solutions. The equilibrium constants and the molar absorption coefficients for a 1:1 complex for MMA-CHOC and for a 2:1 complex for VAc-CHOC are reported. A plausible mechanism for the spontaneous polymerization of MMA in the presence of CHOC is presented. The tacticities of the polymers formed in the presence of CHOC are discussed.
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    Polymerization of aromatic methacrylates to high degrees of conversion (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1571-1576 
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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: Polymerizations of 2,4,6-tribromophenyl methacrylate (1a), p-tolyl methacrylate (1b), p-cyclohexylphenyl methacrylate (1c), and p-methoxyphenyl methacrylate (1d) were carried out up to conversions higher than 99%. The kinetics of the process was followed by the refractometric technique using a He-Ne laser as light source. The influence of the concentration of initiator on the appearing of the gel effect was examined, taking the polymerization of 1a as an example.
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    Influence of the structure of chlorophenyl 2,3-epoxypropyl ethers on their reactivity in ionic polymerization (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1577-1584 
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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: Empirical correlation equations could be derived for comparison of the relative reactivities of a homologous series of chlorophenyl 2,3-epoxypropyl ethers in cationic polymerization initiated by SnCl4, and in anionic polymerization initiated by KOH. These equations include a conformation constant, Sk, accounting for the interaction between the oxirane ring and the aromatic substituent. For the anionic polymerization the saponification number must be introduced additionally into the correlation equation to account for a side reaction between initiator and substituent.
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    Parameters of the generalized exponential function for the molar mass distribution of the polystyrene standard NBS 706 (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1653-1659 
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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 experimental molar mass distribution of the polystyrene standard NBS 706, as determined by high performance size exclusion chromatography, has been fitted with the generalized exponential function, whose parameters have been evaluated by a computer procedure. Comparison is made with the Schulz-Zimm and logarithmic normal distributions, and the consistency of the different average molar masses is discussed.
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    Comparison of methods for determination of the number of active centers in Ziegler-Natta polymerizationsDedicated to Professor Ing. Dr. O. Wichterle on the occasion of his 70th birthday (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1975-1985 
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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: Four intrinsically different methods for the determination of the number of active centers were employed in propylene polymerization catalyzed by the typical heterogeneous system TiCl3/AlEt2Cl: (i) determination of M̄n (GPC method) and calculation of number of macromolecules therefrom; (ii) quenching with BuOT and determination of tritium in the polymer; (iii) quenching with CO or CO2 and determination of carbonyl groups in the polymer (IR spectroscopy); (iv) quenching with SO2 and determination of sulfur in the polymer. The first two methods exhibited a reasonable agreement for the number of active centers. Method (iii) gave much lower values, whereas method (iv) was found to be virtually unsuitable due to a high extent of side reactions of SO2 with the polymer. A similar comparison of the methods was made in ethylene polymerization catalyzed by the typical homogeneous systems Cp2TiEtCl/AlEtCl2 and Cp2TiEtCl/alumoxane. Method (ii) gave a much lower number of active centers than method (i), due perhaps to a low extent of alcoholysis of the Ti—C bond or to a high kinetic isotope effect. CO2 appeared to be entirely inert as a quenching agent and CO had been reported to show side reactions. It follows that none of the above quenching methods have universal application and thus literature data should be considered with caution.
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    Vinyl polymers with aromatic substituents, 2Part 1: cf.2. Polymerization of 9-allylanthracene and structures of the polymers (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 2033-2040 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Radical, cationic, and Ziegler-Natta polymerizations of 9-allylanthracene (1) were carried out. The radical polymerization was found to be an inefficient method leading to oligomers with complex structure. Reaction of initiator radicals and growing macroradicals with the anthryl group or with the allylic hydrogen leads to resonance stabilized radicals which stop the polymerization. The cationic and Ziegler-Natta polymerizations gave a copolymer with 9-anthrylmethylethylene units (8) (from normal 1,2 addition) and 9,10-anthrylenepropylene units (11) (from the electrophilic attack of carbocations at the aromatic nucleus). Low polymerization temperatures lead to a preference for the alkylation reaction.
    Additional Material: 3 Ill.
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    Metalloester, 109. Mitteilung: cf.1. Die in den Veröffentlichungen Metalloester 9 and 10 enthaltenen Ergebnisse wurden auf dem V. Internationalen Mikrosymposium über «Fortschritte in den Ionenpolymerisationen» in Prag, im Juni 1982, vorgetragen. Untersuchung des anfangsstadiums der anionischen polymerisation von methylmethacrylat. einfluß von reaktionsbedingungen auf die umsetzung von methyl-2-sodioisobutyrat mit methylmethacrylatProf. Dr. Otto Wichterle zu seinem 70. Geburtstag gewidmet (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 2021-2031 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: In continuation of a preceding study, the course of the reaction between methyl methacrylate (2) and methyl 2-sodioisobutyrate (1) was investigated, applying reaction times between 0,02 and 1,4 s, as a function of the following conditions: character of the solvent, effect of the addition of sodium tert-butoxide, mole ratio 2/1, concentration of the reactants, and temperature. Under all conditions used, the reaction between 2 and 1 was very fast and gave rise, along with other compounds, to a mixture of oligomers of 2 with the average molecular weight obeying the ratio [2]:[1]eff.. The balance of products showed that in some cases only a part of 1 has reacted with 2, giving rise to the expected oligomers. The efficiency of 1 varied in the range from 24 to 100%, being mainly dependent on the character of the solvent (efficiency in THF 〉 in toluene). Moreover, it was higher in the presence of sodium tert-butoxide and with a higher 2/1 mole ratio. In experiments with a low efficiency of 1 a certain part of it remained unreacted, in spite of the presence of 2, for reasons not yet clear. The resulting oligomers undergo consecutive reactions. Starting with the trimer 3b, cyclizing selfcondensation was the most important of the consecutive reactions and could be easily investigated in the case of the trimer. The rate of this cyclization was much higher in THF than in other solvents used, and it was, therefore, difficult to obtain the linear trimer at room temperature. On the contrary, the addition of sodium tert-butoxide or lowering the temperature suppressed the cyclization, which was especially easy to perceive in THF. Using the experience described in the study, it is possible to choose such conditions of the reaction between 1 and 2, under which the required oligomers are formed in good yield.
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    Hydrodynamic crossover in two-polymer mixtures from viscosity measurements (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 2153-2158 
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    Notes: A very sharp crossover is observed in the variation of the reduced viscosity ηsp/c as a function of the concentration c for mixtures of 1:1 by weight mixtures of polystyrene and poly(methylmethacrylate) in benzene at 20°C and a 1:1 by weight mixture of poly(ethylene glycol) and polystyrene in benzene at 20°C. The crossover is attributed to the critical to the concentration of the two respective polymers in the solution and its sharpness is due to the incompatibility between the two different polymers.
    Additional Material: 4 Ill.
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    Preliminary results on ethylene/propene copolymerization in the presence of Cp2Ti(CH3)2/Al(CH3)3/H2O (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 2193-2198 
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    Notes: Ethylene/propene copolymerizations were carried out in the presence of the catalyst system Cp2Ti(CH3)2/Al(CH3)3/H2O (Cp = cyclopentadienyl group), and the reactivity ratios r1, r2 were determined through the Fineman and Ross equation and via 13C NMR. A nearly alternating copolymer structure was pointed out. The yields as well as the molecular weights of the copolymers strongly decrease with increasing propene mole fraction in the copolymers.
    Additional Material: 2 Ill.
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    Lichtinitiierte polymer- und polymerisationsreaktionen, 10Teil 9: cf.21.. Photoinduzierte zersetzung von diareniodonium- und triarensulfoniumsalzen durch kaliumtrisoxalatoferrat (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 2409-2419 
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    Notes: In order to elucidate kinetics and mechanism of photoinitiation processes based on potassium trioxalatoferrate(III) (K3[Fe(cx)3])/ onium compounds/acrylamide (AA) interactions, photolysis and stationary photopolymerization were carried out. Diphenyliodonium chloride (Ph2I⊕Cl⊖) and triphenylsulfonium tetrafluoroborate (Ph3S⊕BF⊖4) were used as onium compounds. These compunds react with photolytically formed ·CO⊖2 radicals by an electron transfer mechanism. The resulting phenyl radicals were detected by spin trapping with nitrosodurene. The quantum yield of the decomposition of onium salts, φIn, depends both on their reduction potentials and concentrations. Thus, an efficient redox reaction between ·CO⊖2 radical and Ph3S⊕BF⊖4 is impossible because the former reacts faster with the Fe(III) complex. The ratio between rate constants of these competitive reactions (onium compound/Fe(III)) are 0,1 (Ph2I⊕Cl⊖) and 4 · 10-4 (Ph3S⊕BF⊖4). Only with the system K3[Fe(ox)3]/Ph2I⊕Cl⊖/AA a radically induced photopolymerization was observed. Both the rate and the quantum yield (φBr) depend on the Ph2I⊕Cl⊖ concentration. A correlation between φBr and √φIn was found.
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    Synthesis and characterization of some new polyamides containing azomethine groups in the polymer backbone, 2Part 1: cf.7. (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 2447-2455 
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    Notes: New aromatic polyamides containing azomethine groups in the backbone and also having different linking groups like —CH2—, —CH2—CH2—, and —O— were synthesized by reacting 4,4′-[1,4-phenylenebis(methylidynenitrilo)]dibenzoyl dichloride (2) with some diamines 1a - d, 4, and 6 by the low temperature solution polycondensation method. The physical, spectral, and thermal properties of the synthesized polyamides were investigated. The effect of the nature of different linking groups on the properties of these aromatic polymides was explored by comparing their spectral and thermal data.
    Additional Material: 6 Ill.
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    Aqueous gel permeation chromatography of electrolytes and polyelectrolytes, 2Part 1: cf. 10.. Donnan salt exclusion effectDedicated to Professor Dr. H.-J. Cantow on his 60th birthday (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 2593-2601 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: The salt exclusion of electrolytes and polyelectrolytes in aqueous GPC was investigated theoretically and experimentally, in order to elucidate the feasibility of GPC as a technique for measuring the Donnan salt exclusion parameter, Γ¯, of polyelectrolytes. Three simple salts different in the valency of the anion, i.e., sodium chloride, sodium sulfate and naphthalene-1,3,6-trisulfonic acid trisodium salt, were eluted with aqueous NaNO3 solution on a Sephadex G-10 gel column. The experimental results were analyzed in terms of the Donnan equilibrium established on the gel, and the Γ¯ value of these simple salts was evaluated. It was found that the Γ¯ value from GPC was in good agreement with the theoretical value of 1/2 for an ideal case, showing that the colligative properties of electrolytes and polyelectrolytes such as Γ¯ can be accurately investigated by means of GPC. GPC experiments on the Donnan salt exclusion were further carried out for the heparin-NaCl system by using a Sephadex G-25 gel column. From the experimental data, the Γ¯ value of heparin was estimated.
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    IR-bandenstrukturanalyse der amidstreckschwingungen von N-methylacetamid als modellsubstanz für makromoleküle mit peptidbindungen (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 2693-2704 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: The C=0 and N—H stretching vibrations of N-methylacetamide in solution were studied at different concentrations and temperatures. By means of bandfitting and using the second derivative, the C=O stretching band (Amide I) was resolved into four component bands. An assignment of these frequencies is discussed. The band splitting of amide I indicates the presence of cis-trans isomerism about the peptide (—CO—NH—) link and a frequency shift of the free C=O end groups of associated molecules. The H-bond enthalpy seems to be influenced by the chain length of the associates.
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    Degradation and depolymerization of poly(propylene carbonate) by diethylzinc (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 907-912 
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    Notes: Poly(propylene carbonate) (PPC) was treated with diethylzinc in 1,4-dioxane solution at 30°C, Zn(C2H5)2 being used in excess or defficiency with regard to carbonate units. PPC was found to undergo degradation and depolymerization reactions, which were followed via the polymer intrinsic viscosity and the propylene carbonate yield. A model reaction between diethyl carbonate and diethylzinc was carried out too. From the results, a mechanistic view for both pathways, degradation and depolymerization, is proposed.
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  • 50
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    Immobilisation du complexe de nickel de l'histidine L(+) sur des supports macromoléculaires hydrophiles (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 9-16 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: N-(4-vinylbenzyl)-L-histidine (5) and the corresponding methyl ester were synthesized by reacting L-histidine or L-histidine methyl ester with 4-formylstyrene. N-(4-vinylbenzyl)-L-histidine methyl ester was radically copolymerized with various amounts of 2-hydroxyethyl methacrylate and ethylene dimethacrylate, leading to resins of different degrees of hydrophilicity and crosslinking. After saponification of the histidine ester groups, the resins were chelated with Ni2+ salt in order to be used as polymeric catalysts in enantioselective ester hydrolysis reactions.
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    Hydrolyse énantiosélective d'α-aminoesters catalysée par des complexes chiraux de métaux de transition immobilisés sur supports macromoléculaires (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 17-28 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: The kinetics of hydrolysis of D- and L-histidine methyl ester were studied in the presence of crosslinked hydrophilic polymeric supports bearing L-histidine moieties complexed with Ni2+ salt. The selectivity of hydrolysis (kD/kL ratio) rises with the increase of the hydrophilic character (content of monomeric units of 2-hydroxyethyl methacrylate) of the resin. It varies with the ratio ester / catalytic moiety, the best result being obtained when the latter is close to 1. The selectivity depends on the temperature and an inversion of this selectivity is observed at 31°C. The optimization of all the parameters studied allowed to reach the same enantioselectivity and comparable rates of hydrolysis as observed in a model reaction carried out under homogeneous conditions.
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    Hochdruck-hochtemperatur-reaktionen in einem strömungsreaktor, 1211. Mitteilung: cf.1. Thermische dimerisierung von acrylsäauremethylester, methylvinylketon und acrylnitril (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 63-69 
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    Notes: Thermal dimerization of methyl acrylate to dimethyl 2-methyleneglutarate was performed in a high pressure-high temperature flow apparatus at temperatures up to 420°C and pressures up to 200 bar. The head to head dimer dimethyl 2-methyl-3-methylenesuccinate was observed, too. Methyl vinyl ketone and acrylonitrile are able to dimerize analogously.
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    A statistical analysis for stereo-configurational sequences of vinyl polymers (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 91-104 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: In this paper, the distribution of configurational sequences in vinyl polymers is re-treated theoretically by the aid of statistics. Various Markovian probabilities of multi-ads are listed. A series of relationships among the frequencies of occurrence of n-ads with different configurations is obtained, most of them have not been reported up to now. Finally, a convenient method for determination of the order of a Markovian process is established.
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    Etude de la structure ramifiée du polyéthylène basse densité par viscosité et diffusion de la lumière de fractions issues de la chromatographie d'exclusion gpc (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 135-145 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Fractions of high density polyethylene (PEhd) and low density polyethylene (PEld) obtained from gel permeation chromatography were studied by viscometry and light scattering. The variations of the intrinsic viscosity [η], the molecular weight M̄w, and the radius of gyration Rg for PEhd and PEld were compared with one another and the relationships [η] vs M and Rg vs. M for PEhd were established. The dependence of structural parameters g = (Rg2)branch/(Rg2)linear and g′ = [η]branch/[η]linear on the molecular weight was determined for three samples of PEld.
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    On the principle of equal reactivity in solution polycondensation (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 105-111 
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    Notes: The influence of the degree of polymerization of oligomers (1 ≤ l ≤ 50) on the reactivity of the OH endgroups is exemplified by the reaction of oligoterephthalates of phenolphthalein with benzoyl chloride under ϑ-conditions. It is found that with increasing chain length l the hydroxyl group activity increases according to an S-form law. It is suggested that the ester groups of the macromolecule influence the activity of the OH endgroups due to solvation effects. This suggestion is confirmed theoretically and experimentally.
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    The stochastic kinetics of intramolecular reactions in linear polymers (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 123-134 
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    Notes: This paper deals with the kinetics of reactions of linear flexible macromolecules in solution possessing initially several reactive sites per macromolecule. It is assumed that the reactive sites interact with each other encounter-controlled and that both intra- and intermolecular reactions are possible. On the basis of the theory of stochastic kinetics in microsystems, equations were derived, describing the kinetics of intramolecular reactions as a function of the molecular weight distribution. An important application of this theoretical treatment pertains to the distribution between inter- and intramolecular reactions. A demonstration for typical reaction conditions reveals the influence of rate parameters and of the average number of reactive sites per macromolecule r̄(0) on the proportionate distribution expressed by fA = f (r̄(0)); (fA = fraction of intramolecular reactions). This function is only weakly influenced by varying the width parameter β in the case of Schulz-Zimm molecular weight distributions from β = 1 to → ∞.
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    Crystallization of polydisperse polyethylene fractionated according to pennings' method (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 225-232 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: It is shown that the molten state and the semi-crystalline state of polydisperse polyethylene are interrelated. Large polydisperse fractions obtained according to Pennings' fractionation method were studied by small angle X-ray scattering and differential thermal analysis; the long period, depending on the molecular weight distribution, is shown to be given by the weight average end-to-end distance of the coils; the long chains with molecular weights M 〉 105 behave as a series of “sub-chains” with molecular weight M* = 105 which crystallize independently. The same result is found for fractions with narrow molecular weight distribution and for mixtures of polyethylene fractions.
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    Fixation sur cellulose de médicaments libérables par voie enzymatique (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 277-285 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: As an approach to the programmed release of drugs a polymeric carrier (1) from which the drug would be liberated by the degradation of definite covalent chemical bonds by means of specific enzymes, was synthesized by coupling pholcodine (2), an antitussive drug, with an insoluble, physiologically inert polymer, cellulose, using L-phenylalanine as a spacer arm. As chemical bond between drug and amino acid an ester function was chosen linking the hydroxyl group of 2 and the carboxylic end of L-phenylalanine. This linkage is not hydrolyzed in simulated digestive fluids containing pepsin or trypsin; it is only broken in the presence of α-chymotrypsin to release slowly the parent drug.
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    Polymerisationsauslösung mit substituierten ethanen, 54. Mitt. cf. 4.. Polymerisation von verschiedenen methacrylmonomeren (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 287-294 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Methyl methacrylate, benzyl methacrylate, butyl methacrylate, and methacrylic acid can be polymerized by 1,1,2,2-tetraphenyl-1,2-diphenoxyethane and 1,1,2,2-tetraphenyl-1,2-dicyanoethane. In the first period of the polymerization with both initiators oligomers are formed which can initiate the polymerization of other vinyl monomers yielding block-copolymers besides the resp. homopolymers.
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    Absolute determination of molar masses of standard polystyrenes by means of sedimentation-diffusion measurements in cyclohexane (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 295-308 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Accurate measurements of the sedimentation coefficients at unit pressure and zero-concentration s00, the diffusion coefficients at zero concentration D0, and the intrinsic viscosities [η] were conducted at theta-conditions (cyclohexane, 34,5°C) on 11 polystryrene standard samples with narrow molar mass distribution. These samples with nominal mass-average molar masses (5 · 104 〈 Mw 〈 2 · 106 g · mol-1), provided by three manufacturers for the use as calibration standards, were the same as in the previous paper of this series summarizing our measurements in toluene. Logarithmic correlations between s00, D0 and [η] are linear with deviations lower than ± 3% and indicate good consistency of all three independent sets of measured quantities. The molar masses MsD as determined from s00 and D0 by means of the Svedberg equation are in very good accordance with those previously determined in toluene, but for most samples the MsD are lower than the nominal values Mw as given by the manufacturers. For some standards the deviations amount to 15-35% and cannot be explained by experimental errors or by the polydispersity of the samples. On the other hand, two pairs of standards exhibit the same values of s00, D0 and [η] in both solvents, although the nominal molar masses differ by 20%. These results lead to the conclusion that the experimentally determined MsD values are more reliable characteristics of the standard samples than the nominal Mw values and that the sedimentation-diffusion technique is a powerful, though laborious, tool for an absolute determination of the molar mass.
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    Induced optical activity in copolymers of (-)-p-(3-menthyl) acrylate with 4-vinylpyridine (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 233-233 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    URL: http://dx.doi.org/10.1002/macp.1983.021840123
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    International conference “polymer photochemistry” (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 234-234 
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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
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021840124
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    Synthesis and investigation of the properties of cardo-copolyimides with different microstructure (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 235-252 
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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: Copolyimides, their microstructure being determined by the method of synthesis, were prepared by copolycondensation of 4,4′-oxydiphthalic anhydride (1a), 4,4′-carbonyldipthalic anhydride (1b), or 1,8:4,5-naphthalenetetracarboxylic anhydride with a mixture of two diamines, hexa-, octa-, or dodecamethylene diamine (5a, 6a, 7a) and cardo-diamines 9,9-bis(4′-aminophenyl)fluorene (3a) and 3,3-bis(4′-aminophenyl)phthalide (4) or two aromatic diamines, 4,4′-oxydianiline (9) and 2,2-bis(4-aminophenyl)hexafluoropropane (8), at various mole ratios of the comonomers. Blockcopolyimides with five-membered imide cycles were formed by catalytic imidization of the intermediate polymers prepared by addition of the solid dianhydride to a solution of the mixture of the two diamines, whereas the thermal cyclization of such polymers and the one-step high-temperature synthesis led to random copolyimides. The thermal and mechanical properties of the copolyimides with various microstructure and their solubility in organic solvents were compared.
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    Hydrodynamic constants and frictional properties of polystyrene in dilute solution (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 309-317 
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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 data from hydrodynamic measurements on eleven standard polystyrene samples in a poor and a good solvent (cyclohexane at theta-temperature 34,5°C, toluene at 25°C) are analyzed in terms of the two-parameter theory of the hydrodynamic properties of random coils. The discussion is focussed on the expansion factors of hydrodynamic radii αf and αμ, evaluated from the translation friction coefficients and the intrinsic viscosity, and on the hydrodynamic-interaction parameters P and Φ. The expansion factors αf and αη are shown to assume nearly equal values (at 1,15 ≤αη ≤ 1,5). That implies that the dependences on coil expansion must be very similar for P and Φ1/3. The value of the P parameter in the unperturbed state (i.e. P0) is shown to be close to that recently calculated by Zimm and to be significantly higher than the results of previous theoretical calculations.
    Additional Material: 2 Ill.
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    Redox initiators for cationic polymerization: The diaryliodonium Salt/Sn(II) redox couple (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 463-473 
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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: Diaryliodonium salts undergo facile copper catalyzed reduction in the presence of Sn(II) compounds. Such redox couples can be employed for the in situ generation of active initiators for cationic vinyl and ring opening polymerizations. Two mechanisms are proposed for the reduction reaction to explain the stoichiometry of the reactants and nature of the products formed. The polymerizations of several representative cationically polymerizable monomers were studied.
    Additional Material: 6 Ill.
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    Polymerization of isobutene by the inifer technique, 1. Low molecular weight products using 1,4-bis(1-chloro-1-methylethyl)benzene/BCl3 as initiator (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 553-562 
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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 cationic polymerization of isobutene by the “inifer”-technique was studied. Preliminary experiments are described which suggest that useful polymer can be prepared only when BCl3 is rapidly added to the premixed monomer/inifer mixture and that such polymerizations do not go to completion. Some questions regarding the mechanism are discussed and remain open.
    Additional Material: 5 Ill.
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    Molmassenverteilung und lösungszustand von linearen polyethylenen, 1. Lichtstreuungs-, viskositäts- und GPC-messungen (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 585-596 
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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: Light scattering, viscosity and GPC measurements were performed on a homologous series of linear polyethylenes with viscosity average molar masses in decahydronaphthalene at 135°C between 1,0 · 105 and 2,7 · 106 g · mol-1 and relatively broad molar mass distributions. 1,2,4-Trichlorobenzene, α-chloronaphthalene, decahydronaphthalene (decalin) and decane were used as solvents. In the case of linear polyethylene in decahydronaphthalene and decane relationships between intrinsic viscosity and weight average molar mass were established. The values of the weight average molar masses obtained by light scattering are considerably higher than those obtained by viscosity and GPC measurements. These discrepancies are explained by molecular aggregation of the polyethylene macromolecules.
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    Functional monomers and polymers, 103Part 102: Y. Sakuma, Y. Inaki, K. Takemoto, J. Polym. Sci., Polym. Chem. Ed., in press.. Synthetic application of polystyrene-bound chloropyrimidine and chloropurine as dehydrating and desulfhydrating reagents (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 497-503 
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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: Poly{1-[4-(4-chloro-2-oxo-1,2-dihydropyrimidin-1-ylmethyl)phenyl]-ethylene} (1b) was pre-pared by condensation of chloromethylated polystyrene and uracil and subsequent reaction with POCl3, and used as dehydrating and desulfhydrating reagent for the preparation of hydro-xamates, acid chlorides, nitriles, and lactones. Other types of polymeric reagents, poly{1-[4-(2,6-dichloro-4-pyrimidinylaminomethyl)phenyl]ethylene} (4) and poly{1-[4-(6-chloro-9(7)-puri-nylmethyl)phenyl]ethylene} (5) were prepared analogously. It was found that 1 b shows the highest activity in these syntheses as compared with the other polymeric reagents 4 and 5.
    Additional Material: 2 Tab.
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    Vinyl polymerization initiated with systems of dimethylaniline N-oxide and some chlorosilanes (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 519-526 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Binary systems of dimethylaniline N-oxide (DMAO) and some chlorosilanes were found to be effective initiators for vinyl polymerization. The initiating activity of the chlorosilanes decreases in the following order: SiCl4 〉 CH3SiCl3 〉 (CH3)SiCl2 〉 (CH3)3SiCl. The copolymerization of methyl methacrylate (MMA) with styrene, initiated with the system DMAO/SiCl4, propagates via a radical mechanism. The polymerization of MMA with the system DMAO/SiCl4 was investigated kinitically in acetonitrile. The overall activation energy of the polymerization was calculated to be 44,4 kJ/mol, an extremely low value. The initial poly-merization rate(Rp) is of 1st order in monomer concentration. Rp is proportional to the square root of the DMAO concentration, and slightly dependent on the SiCl4 concentration for high SiCl4 concentrations. This suggests that a complex is formed between DMAO and SiCl4. Spec-troscopic results on the system DMAO/SiCl4 also indicate the formation of a complex. A yellow crystalline compound was isolated from the reaction of DMAO with SiCl4 at room temperature in methylene chloride/diethyl ether (1:3, by vol.). The complex has a composition of four moles of DMAO and one mole of SiCl4. From these results and from spin trapping studies, a possible initiation mechanism is proposed for the polymerization initiated with the system DMAO/chlorosilane.
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    Grafting of N-vinylpyrrolidone onto segmented polyurethane initiated by 2,2′-azoisobutyronitrile (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 725-731 
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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: An unsaturated segmented polyurethane was prepared from cis-2-butene-1,4-diol, poly(ethylene glycol), butane-1,4-diol, and methylene bis(4-phenyl isocyanate). Graft copolymerization of N-vinylpyrrolidone onto the segmented polyurethane was studied using 2,2′-azoisobutyronitrile (AIBN) as initiator in DMF as solvent. The graft copolymers were isolated from the homopolymer and the ungrafted polyurethane by selective solvent extraction. The effect of reaction time, temperature, and of monomer and initiator concentrations on the degree of grafting was also investigated. The percent grafting was enhanced with increasing [AIBN] up to 40 mmol.dm-3, but then decreased at higher concentrations. An explanation based on complex formation between the monomer and the urethane linkages in polyurethane is suggested.
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    Polymeric schiff's base chelates and their precursors, 4Part 3: cf.13.. Syntheses of schiff's base chelates from diaminomaleonitrile and investigation of their activity for the valence isomerisation of quadricyclane to norbornadien (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 763-778 
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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: Various low molecular and polymeric Schiff's base chelates 9 - 13, 15 - 19, and 22 were synthesized from Z-2,3-diamino-2-butene dinitrile (3), the corresponding o-hydroxyaldehydes, and Co(II), Ni(II), or Cu(II) acetate. Their IR, UV, and MS data are discussed. The cobalt containing Schiff's base chelates including the polymeric ones, were found to be effective catalysts for the isomerization of quadricyclane (24) into norbornadiene (23). First results are reported.
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    Kinetic determination of stereoselectivity in the anionic polymerization of α-ethyl-α-phenyl-β-propiolactone (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 811-819 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the anionic polymerization of optically active α-ethyl-α-phenyl-β-propiolactone (optical purity 16,8%) initiated with bis(triphenylphosphine)iminium acetate was investigated and the rate constants for the homo-(kph) and crosspropagation (kpc) (considering R and S enantiomers as comonomers) were determined. The knowledge of the values of kph and kpc, equal to 1,53·10-4 and 9,0·10-51· mol-1·s-1, respectively (25°C, CH2Cl2 solvent), allowed us to calculate the distribution of homosequences in the polymer prepared from racemic monomer. The concentration of homosequences was slightly higher than calculated for the process with random enchainment of enantiomers. Thus, the content of homodyads, homotriads, and homotetrads equals 63, 40, and 25%, whereas for the random process it was 50, 25, and 13%, respectively. This difference is, however, too small to create homoblocks which could be responsible for the observed crystallinity of these polymers.
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    Polyvinylpyridine complexes of ruthenium(III) chloride (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 613-625 
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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 polymeric materials were prepared by reacting poly(2021840311vinylpyridine) or poly-(4-vinylpyridine) with ruthenium (III) chloride in refluxing methanol. Mole ratio of RuCl3 to vinylpyridine (Ru: PVP ratio) was varied from 2:1 to 1:20. From IR and UV/VIS spectroscopic data it is shown that several kinds of ruthenium-PVP complexes are present, their relative proportions depending on the Ru: PVP ratio of the original reaction mixture and on the reaction time. The spectroscopic properties of the polymer complexes are compared to those of methylpyridine complexes of ruthenium(III) chloride.
    Additional Material: 6 Ill.
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    Structural studies on molecular complexes of polyethers, 1. Urea-ethylene oxide oligomer complexes (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 669-674 
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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: Complexes of urea with ethylene oxide oligomeric mixtures were investigated by X-ray diffraction, IR-absorption, and differential scanning calorimetry. A new crystal modification (Form II) was found for the complexes of urea with ethylene oxide oligomers whose number average molecular weights ranged from 400 to 1000. The Form II complex has a tetragonal unit cell (a = 7,30 Å, c = 19,51 Å), containing eight molecules of urea and eight ethylene oxide units. This modification is metastable. A solid-solid transition to the conventional Form I crystal occurs on heating up to a temperature between the melting points of both forms. The dependence of the melting points of these complexes on the molecular weight of the oligomers was also studied.
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    Polymères porteurs de dérivés du glycérol, 1. Polymérisation du méthacrylate d'époxy-2,3 propyle et du méthacrylate-phényl-2 butyrate d'hydroxy-2 triméthylène (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 681-689 
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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: Radical polymerizations and copolymerizations of 2,3-epoxypropyl methacrylate (1) and its reaction product with 2-phenylbutyric acid (2), 2-hydroxytrimethylene methacrylate 2-phenylbutyrate (3), were studied using 2,2′-azodiisobutyronitrile, benzoyl peroxide, or H2O2 (with UV irradiation) as initiators, and also the influence of the experimental conditions (temperature, concentration, time) on the yield. Due to the reactivity of the oxirane moiety, poly(2,3-epoxy-propyl methacrylate) can easily be modified by ring opening reactions, e.g. with carboxylic acids.
    Additional Material: 6 Ill.
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    Free radical polymerization of water-soluble vinyl monomers in the two-phase (water/organic) system using methylated β-cyclodextrins as initiator-carriersPart of this work was presented as preliminary communications in our previous papers1. (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 925-933 
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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 the polymerization of water-soluble vinyl monomers, such as acrylamide, sodium p-sty-renesulfonate, acrylic acid, and methacrylic acid, using water-insoluble free radical initiators such as azo or peroxide compounds in the two-phase system consisting of water and an organic solvent (chloroform/ligroin, volume ratio 1:4), the addition of a small amount of a methylated β-cyclodextrin, heptakis(2,6-O-dimethyl)-β-cyclodextrin (DM-β-CD) or heptakis(2,3,6-O-trimethyl)-β-cyclodextrin (TM-β-CD), was found to cause a marked increase in conversion of the polymerization. Based on this finding, it may be suggested that the methylated β-cyclodextrins act as initiator-carriers which transport the water-insoluble initiators from the organic phase to the aqueous phase to initiate the polymerization of water-soluble vinyl monomers.
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    Polyurethanes containing poly(oxyethylene) block units and their properties as polychelatogenes (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 969-976 
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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: Polyurethanes 6 and 7 based on poly(oxyethylene) (5) were synthesized and investigated for the application as macromolecular chelating agents. 4,4′-Diaminobenzil (3c) and 4,4′-diaminobenzil monoxime (4a) were prepared as monomer precursors in 70 and 80% yield. Copolymers were obtained in yields between 40 and 60% by polyaddition of the corresponding diisocyanates 3d and 4b to poly(oxyethylene) (5) of different chain length and characterized by IR and 13C NMR spectroscopy. The application of the resulting polyurethanes containing functional aromatic block units as polychelatogenes was studied in homogeneous phase by membrane filtration. The metal content was determined in both the filtrate and the retentate and in the case of Ni2+ at different pH values. At pH 2, for example, the molar binding capacity of a polyurethane sample of 6 was 3 times as high as that of 5.
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    Determination of absolute rate constants for radical polymerization and copolymerization of ethyl α-cyanoacrylate in the presence of effective inhibitors against anionic polymerization (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1025-1033 
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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 absolute rate constants of propagation kp and of termination kt of ethyl α-cyanoacrylate (ECNA) were determined in bulk at 30°C by means of the rotating sector method under conditions to suppress anionic polymerization; kp = 1 622 1 · mol-1 · s-1 and kt = 4,11 · 108 1 · mol-1 · s-1 for the polymerization in the presence of acetic acid, and kp = 1610 1 · mol-1 · s-1 and kt = 4,04 · 108 l · mol-1 · s-1 for the polymerization in the presence of 1,3-propanesultone. The magnitude of kp2/kt determined was 6,39 · 10-3 l · mol-1 · s-1. The absolute rate constants for cross-propagation in ECNA copolymerizations were also evaluated. Quantitative comparison of the rate constants with those of common monomers and polymer radicals shows that the strong electron-withdrawing power of the ethoxycarbonyl and cyano groups enable the poly(ECNA) radical to add to monomers as fast as the other polymer radicals. The relatively high reactivity of ECNA, regardless of the type of attacking polymer radical, is interpreted by a transition state greatly stabilized by both the ethoxycarbonyl and the cyano groups.
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    Polymerization of acrylonitrile initiated by the redox system manganese (III) acetate/ethylene glycol (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1121-1128 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of polymerization of acrylonitrile initiated by the redox system manganese (III) acetate/ethylene glycol was studied in aqueous sulfuric acid medium in the temperature range from 30 to 40°C. The effect of varying the concentrations of monomer (M), acetic acid, and sulfuric acid and the addition of some electrolytes on the rate of polymerization (Rp) was investigated. Based on the experimental observations of the dependence of (Rp) on various parameters, a suitable kinetic scheme could be proposed. The plot of Rp2[M]2 vs. [M] was found to be linear, a striking general phenomenon observed for all the substrates we have studied in this laboratory.
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    Polymerization of ethylene oxide catalyzed by triphenylstibine oxide (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1163-1169 
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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: Polymerization of ethylene oxide (EO) and propylene oxide (PO) catalyzed by two types of triphenylstibine oxide ((C6H5)3SbO, TPSO) was investigated. The polymeric and high melting point triphenylstibine oxide (TPSOa) was found to be active, but it shows a long induction period in the polymerization at 80°C. During the induction period, TPSOa is probably cleaved into an active antimony species by interaction with EO. TPSOa is activated by addition of some O-containing compounds such as ethanol, 1,4-dioxane, or water. Monomeric and low melting point triphenylstibine oxides (TPSOb and TPSOc) were found to be inactive. Their activity markedly increases by addition of Lewis bases such as triphenylphosphine. The difference in the activity of TPSOa and TPSOb or TPSOc is considered to result from differences in aggregation.
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    The cationic polymerisation of 2-alkenylfurans, 3Part 2: cf. 2.. Spectroscopic study of the alkylation as important side reaction leading to branched products (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1189-1211 
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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 spectroscopic (UV, IR, 1H NMR) study of the cationic polymerisation of 2-vinylfuran (1a) and 2-isopropenylfuran (2a) showed the existence of an important alkylation reaction at C5 which competes with normal propagation. The extent of this competition depends on the monomer used and the polymerisation temperature. A comparison of the spectra of standard polymers (prepared by radical or stereospecific polymerisation) with those of polymers obtained by cationic initiation allowed to assess the extent of alkylation and its regiospecificity at C5 2-Methyl-5-vinylfuran (1b) and 2-methyl-5-isopropenylfuran (2b) were found to undergo cationic polymerisation without any interference from alkylation reactions. Reactions between these four monomers and 2-methylfuran in the presence of typical acidic catalysts gave very high yields of alkylated products and no polymerisation, thus confirming the importance of this electrophilic reaction and its possible application to synthetic uses.
    Additional Material: 15 Ill.
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    Aliphatische azoverbindungen, 1413. Mitteilung: C. Rüchardt, M. Schmittel, A. Schulz, Chem. Ber. 114, 3533 (1981).. Eine kinetische analyse des thermischen zerfalls aliphatischer azonitrile (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1235-1242 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Ketenimines 4 are known to be formed in a side equilibrium during the thermal decomposition of azonitrile initiators 1, as e.g. 2,2′-azoisobutyronitrile (1a). The concentration of 4 was monitored by IR during the decomposition reaction of 1, and the final yield ratio of substituted succinonitrile 3 and nitrile 5 was determined by GC. Together with the rate constant k1 of 1, these data suffice for calculating k-3, the rate of decomposition of 4, and k3/k2 the rate ratio of the two possible modes of dimerisation of α-cyanoalkyl radicals 2.
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    Singlet oxygen quenching by polyconjugated polymers derived from acenaphthene and acenaphthylene (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1275-1278 
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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: Singlet oxygen quenching by polymers derived from acenaphthene and acenaphthylene is investigated by the oxidation of cis-1,4-polybutadiene with photochemically generated singlet oxygen. It is found that only the polymers with conjugated double bonds in the main chain, poly (1,2-acenaphthenediylidene) (1) and poly (1,2-acenaphthylenylene) (2), are singlet oxygen quenchers. Poly(1,2-acenaphthenylene) (3), with a saturated main chain, is no singlet oxygen quencher. Polymer 2 does not react with singlet oxygen. This is an indication that the quenching mechanism is a physical process.
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    High temperature demixing of poly(decyl methacrylate) solutions in isooctane and its pressure dependenceHerrn Prof. Dr. H.-J. Cantow mit den besten Wünschen zum 60. Geburtstag gewidmet. (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1303-1309 
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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: Solutions of poly (decyl methacrylate) in isooctane (2,2, 4-trimethylpentane) show lower critical solution temperatures (LCST) that lie well below the thermal degradation of the polymer. The corresponding exothermal theta-temperature (from the Shultz-Flory plot) amounts to 210°C. The increase in solvent quality by pressure turns out to be very pronounced (d Tc/dp ≈ +1 K/bar). With solutions of the polymer in motor oils, high temperature demixing is unlikely to occur below their boiling point. The theoretical evaluation of published experimental data for 11 different systems exhibiting LCSTs demonstrates the following: Under the equilibrium vapour pressure of the solution high temperature demixing is generally observed withing the temperature interval between Tb, the boiling point of the pure solvent (1 bar), and 1,5 Tb. As Tc - Tb increases, the heats of mixing and the pressure influence on Tc increase, too.
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    Synthèse de polysiloxanes organofonctionnels, 3Partie 2: cf.1.. Les poly[(acétoxyméthylméthyl)siloxane]s et leurs modèles (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1331-1338 
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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 capability of halogen displacement by metallic acetates in oxyhalomethylmethylsilanediyle units was studied on linear and cyclic model compounds and on homogeneous and heterogeneous polysiloxanes. By displacement of iodine oxyiodomethylmethylsilanediyle units were specifically and quantitatively transformed into acetoxymethylmethylsiloxane units. This displacement was found to be accompanied by rearrangement of siloxane linkages, however, cleavage of substituted methyl and of vinyl groups, as observed in the displacement of chlorine in oxychloromethylmethylsilanediyle units, was not observed.
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  • 86
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    Activation of poly[N-(2-hydroxypropyl)methacrylamide] for the binding of bioactive molecules, 1. Activation with 4-nitrophenyl chloroformate (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1339-1344 
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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: Proper reaction conditions were determined for the activation of water-soluble, biocompatible poly[N-(2-hydroxypropyl)methacrylamide] (1) by esterification with 4-nitrophenyl chloroformate (2). The rate constants of hydrolysis and aminolysis of the 4-nitrophenyl ester groups in resulting polymer 3 were compared. It was shown that at pH 8 - 9 the rate of aminolysis in water solutions is high enough for binding bioactive molecules via —NH2 groups. Cobra venom acetylcholinesterase was bound to the activated polymer 3 and thermostability and immunogenicity of this product were studied.
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    Synthèse par voie radicalaire de polymères à extrémités hydroxylées, 12Partie 11: cf.1.. Etude de la copolymérisation du méthacrylate de méthyle avec divers acrylates et méthacrylates. Détermination des microstructuresCet article est dédié au Professeur Dr. H.-J. Cantow à l'occasion de son 60ème anniversaire (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1379-1388 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Methyl methacrylate was copolymerized with butyl or isobutyl acrylates, and butyl, isobutyl, or 2,3-epoxypropyl methacrylates, by hydrogen peroxide, in the presence of ethanol under UV irradiation (at 254 nm) at room temperature. The analysis of the microstructures was based on resonance splitting of the methoxy protons of MMA, depending on their environment. This splitting was not obtained with isobutyl and 2,3-epoxypropyl methacrylates. All the products were found to be predominantly syndiotactic.
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    Secondary structure of peptides, 11Part 10.: J. Stulz, D. Müller, H. R. Kricheldorf; Makromol. Chem. 184, 1311 (1983).. How to synthesize helical poly(L-phenylalanine)? (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1407-1421 
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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: Polymerizations of L-phenylalanine-N-carobxyanhydride(L-Phe-NCA) were conducted under various reaction conditions and the secondary structure of the resulting solid poly(L-phenylalanine)s was examined by means of 50,3 or 75,4 MHz 13C NMR CP/MAS spectra. When primary alkylamines were used as initiators only α-helix contents ≤ 60% were obtained regardless of solvent and temperature. However, a part of the β-sheet structures was thermodynamically unstable and could be converted into α-helices by reprecipitation. An α-helix content 〉 90% was achieved only when weakly nucleophilic reagents, such as aromatic amines or water, were used as initiators in methylene chloride. A kinetic explanation of these results is discussed. Aprotic bases gave low yields of poly(L-phenylalanine) and substantial amounts of low molecular weight side products. An α-helix content ≥ 95%, was achieved when L-Phe-NCA was polymerized in pyridine at 100°C. The usefulness of IR spectra for the characterization of the secondary structure of poly(L-phenylalanine) is discussed.
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    The compatibility of poly(butyl acrylate) with chlorinated polyethylene (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1459-1468 
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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 compatibility of poly(butyl acrylate) (PBA) with chlorinated polyethylene (CPE) was studied using dynamic mechanical measurements and light scattering turbidimetry. For around 50 wt.-% and above chlorination of CPE they were found to be miscible and show a lower critical solution temperature upon heating. It was found that a favourable heat of mixing of oligomeric analogues could not be taken as a guarantee of the compatibility of the corresponding polymers: the heat of mixing of PBA with cereclor 45 (chlorinated paraffin, 45, 7 wt.-% CI) is negative, but the corresponding polymers PBA/CPE3 (48,0 wt.-% CI) are immiscible. When the Flory equation of state theory is applied to the system, a large negative interaction entropy parameter Q12 must be introduced to counterbalance the large negative interaction energy parameter X12, obtained from the heats of mixing of PBA with cereclor. The simulated spinodals are flat-bottomed. However, if a much smaller negative X12 is adopted, the spinodal calculated will have more curvature. Kinetic constraints on the migration of molecules during phase separation were observed when the molecular weight exceeded certain limits and this could affect the observed cloud point diagram.
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    Potentiometric titration of syndiotactic methacrylic acid/dimethacryloylamine copolymers (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1497-1508 
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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 potentiometric titration of syndiotactic methacrylic acid/dimethacryloylamine (MMA-MAI) copolymers is investigated. In contrast to copolymers studied before, MAA-MAI copolymers possess a highly syndiotactic backbone structure, a compositional statistics known from NMR-measurements, and a cyclic structure as a part of the chain. The statistics of the MAA-units and MAI-rings is nearly random with respect to the formation of imide rings, the rings introducing a trans and a gauche conformation for each ring. Plots of the apparent pK (pKapp) versus the degree of ionization α, or versus log [(1- α)/ α], indicate a change from a relatively dense coil (a-state) to an extended coil (b-state) when α is increased. The decisive parameter for pKapp in the b-state and for the conformational transition of the a-state to the b-state is the charge density on the chain β. The transition takes place for all copolymer compositions in an interval of Δβ ≈1 but the interval is situated at lower absolute values of β for the copolymers with higher contents of MAI-rings. The Δβ at lower β may be either due to a decrease in intramolecular attraction or to a higher electrostatic repulsion. The free enthalpy of the conformational transition is, however, approximately the same for copolymers with different MAI contents. This constancy of the free enthalpy points to a conformational transition which is energetically not much different for the MAA- and the MAI-units in the chain.
    Additional Material: 8 Ill.
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    Metathesis degradation of polymers obtained by grignard-wurtz reaction of partially α-brominated 1,4-polybutadiene (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1561-1569 
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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: 1,4-Polybutadiene was partially brominated at the methylene groups with N-bromosuccinimide. Then, by means of Grignard-Wurtz reactions, the following substituents were introduced: isopropyl, butyl, pentyl, cyclohexyl, phenyl, 4-methylphenyl, 4-ethylphenyl, 3,4-dimethylphenyl, 4-isopropylphenyl, 4-fluorophenyl, 3-trifluorophenylmethyl, 4-chlorophenyl, benzyl, 2-methylbenzyl, and 4-methylbenzyl. The modified polymers (ca. 20% of the units substituted) were degraded to low molecular products with E-4-octene in the presence of the catalyst WCl6/(CH3)4Sn. The degradation products were separated by gas chromatography and identified by mass spectrometry. Isomeric substituents, isomeric units, and isomeric segments in the polymers could be distinguished.  -  In Grignard-Wurtz reactions, transfer reactions with toluene as solvent and simultaneous reactions with two Grignard reagents (4-methylphenyl and 4-methylbenzyl compounds) were also investigated.
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    Functional monomers and polymers, 106Part 105: cf. K. Kondo, Y. Miwa, K. Takemoto, Makromol. Chem. 184, 1171 (1983).. Enantioface differentiation by using chiral polymers derived from ( - )-2-exo-hydroxy-3-bornanone (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1547-1554 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Chiral polymers containing 2,3-exo-dihydroxy-3-endo-p-tolyl-3-bornyl groups prepared by reaction of lithiated polystyrenes with (-)-2-exo-hydroxy-3-bornanone (3), were treated with lithium aluminium hydride to yield products which can be used as reducing reagents. Asymmetric reductions of carbonyl compounds with LiAIH4 were carried out in the presence of both the chiral polymeric and 3-endo-p-tolyl-2,3-exo-bornanediol (4) as low molecular model compounds and the resulting enantiomeric excess was compared. The chiral polymers derived from 3 were found to be effective catalysts for the asymmetric reduction. The enantiomeric excess tends to increase with decreasing degree of crosslinking of the chiral polystyrene resins, exhibiting a high enantioselectivity in the case of chiral linear polystyrenes.
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    Modifizierte ionenaustauscherharze  -  synthese und eigenschaften, 2Mitteilung: cf.1.. Synthese sulfoethylierter und sulfopropylierter styrol-divinylbenzol-harzeHerrn Prof. Dr. H. J. Cantow zum 60. Geburtstag gewidmet (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1585-1596 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Sulfomethylated and sulfopropylated resins were prepared by polymer analogous reactions, starting from macroporous poly(styrene-co-divinylbenzene) matrices. Different reaction paths were used in the synthesis. It could be shown that sulfoalkylation can be achieved directly by reaction of the polystyrene resins with sultones. Alternatively, haloalkylated matrices were prepared and by halogen/sulfo-substitution the corresponding ion exchange resins.
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    Polybutadiène hydroxytéléchélique, 6Partie 5: cf. J. Gonzalez de la Campa, Q. T. Pham, Makromol. Chem. 182, 1415 (1981).. Cinétiques et thermodynamique de condensation de quelques monoalcools et du polybutadiéne hydroxytéléchélique anionique avec les monoisocyanates en l'absence de catalyseur (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1669-1683 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The kinetics and thermodynamics of the spontaneous condensation between monoalcohols (trans-2-hexene-1-ol, 1-octanol, geraniol) and commercial hydroxytelechelic polybutadiene G1000 with propyl isocyanate and phenyl isocyanate in toluene were examined. In all the condensations studied, the third order law is fulfilled. Deviations from the second order law are observed for conversions higher than 60 to 80%. In all cases, autoassociation of the alcohols plays an important role. The rate constants increase with decreasing concentration of hydroxyls and autocatalysis is noticeable. In comparison with the monoalcohols, the different behaviour of the G1000 diol should be due to its trend to be strongly associated by its two hydroxylated chain ends.
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    Structural investigations on cellulose tricarbanilate: Conformation and liquid crystalline behaviourDedicated to professor Dr. H.-J. Cantow on the occasion of his 60th birthday (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1749-1760 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The phase behaviour of cellulose tricarbanilate (CTC) in ethyl methyl ketone (MEK) solutions was studied in the concentration range of 0,2 - 0,8 g/ml as a function of the temperature. By analyzing the textures in the polarizing microscope and by differential scanning calorimetry experiments several different phase transitions and mesophases were detected. At a concentration below 0,6 g/ml CTC in MEK, phase transitions were observed from the crystalline through a liquid crystalline (cholesteric) to the isotropic state. At concentrations higher than 0,6 g/ml, a different behaviour of the CTC solutions was detected and several transitions were found, but only the cholesteric-isotropic transition could be identified. The concentration dependence of the cholesteric-isotropic transitions was determined over the whole concentration range. The conformation of the CTC molecule was studied and a stiff, almost cylindrically shaped 3/2 helix with a repeat distance of 15,25 Å is proposed.
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    Polymerization of methyl methacrylate initiated by a Rh(I) complex and benzoyl peroxide (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1901-1906 
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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 polymerization of some vinyl monomers initiated by carbonylchlorobis(triphenylphos-phine)rhodium(I) (RhCl(CO)(P(C6H5)3)2) and benzoyl peroxide (BPO) was studied. The polymerization ability was found to decrease in the following order: methyl methacrylate (MMA) 〉 styrene 〉 vinyl acetate 〉 isobutyl vinyl ether. In the polymerization of MMA, the average molecular weight increases with an increase in monomer conversion. On the basis of the kinetic studies of the polymerization of MMA initiated by RhCl(CO)(P(C6H5)3)2 and BPO (the mole ratic [BPO]/[RhCl(CO)(P(C6H5)3)2]) was between 1 and 7, the rate of polymerization, Rp' can be expressed by the following equation: \documentclass{article}\pagestyle{empty}\begin{document}$$R_{\rm p} = k\left[ {{\rm RhCl}\left( {{\rm CO}} \right)\left( {{\rm P}\left( {{\rm C}_6 {\rm H}_5 } \right)_3 } \right)_2 } \right]^{0,25} \cdot \left[ {{\rm BPO}} \right] \cdot \left[ {{\rm MMA}} \right]$$\end{document} The overall activation energy for the MMA polymerization was found to be 75,3 kJ/mol within the temperature range of 50 to 80°C. The composition curve of the copolymerization of styrene with MMA using RhCl(CO)(P(C6H5)3)2 and BPO agrees with that of the ordinary radical polymerization. On the basis of these results the initiation mechanism is discussed.
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    The solid-state polymerization, physical properties, and crystal structures of diacetylene mixed crystalsDedicated to Prof. Dr. H.-J. Cantow on the occasion of his 60th birthday (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1945-1955 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Suitable substituted diacetylenes, 2,4-hexadiynylene di-p-toluenesulfonate (1a) and 2,4-hexadiynylene di-p-fluorobenzenesulfonate (1b), were cocrystallized to form substitutional solid solutions. By solid state polymerization of mixed crystals of 1a and 1b single crystals of the corresponding copolymers were obtained. The polymerization rate can be varied over a wide range by admixture of the comonomer 1b in the lattice of 1a. The crystal structures of monomer 1b and of the corresponding polymer, 2b, were determined. It was found that the packing of the reactive triple bond systems is identical in both monomers. Comonomer 1b acts as a defect site with a high probability of chain termination.
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    Polymerization of lactams, 64Part 63: cf.22. Nonactivated anionic polymerization of 2-pyrrolidone in the presence of quaternary ammonium cationsDedicated to Professor O. Wichterle on the occasion of his 70th birthday (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1987-1996 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of addition of quaternary ammonium halides was studied in the nonactivated polymerization of 2-pyrrolidone (1) initiated with the potassium salt of 2-pyrrolidone (2-oxo-1-pyrrolidinylpotassium) (2). The polymerization was accelerated upon small additions of Me4NCl, whereas addition of Et4NBr and Bu4NBr rather had a retardation effect and reduced the molecular weight of polymer. The formation of the corresponding quaternary ammonium salts of 2-pyrrolidone in situ is analogous to the formation of the pure salts in their synthesis from the ammonium halides. The nonactivated polymerization of 1 initiated with the pure tetramethylammonium salt of 2-pyrrolidone (3) showed all kinetic features of other nonactivated polymerizations of 1. High yields and molecular weights of poly(2-pyrrolidone) and a higher number of growth centers during polymerization are evidence of a higher dissociation of 3 dissolved in 1 in comparison with 2 as the initiator. The activation energy of polymerization activated with 3 (47,9 kJ · mol-1 in the range 35 to 55°C) and the reaction order with respect to 3 (1,3 at 45°C) were determined.
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    Hydrolysis of phenyl esters catalyzed by alternating copolymers containing imidazolyl and carboxyl groups (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 2041-2047 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The alternating copolymer, poly(N-vinylimidazole-co-maleic acid) (4), and the random copolymer, poly(N-vinylimidazole-co-acrylic acid) (5), with nearly the same ratio of carboxyl groups to imidazolyl groups, were found to catalyze the hydrolysis of 3-acetoxy-N-trimethyl-anilinium iodide (1), 4-nitrophenyl acetate (2), and 4-acetoxy-3-nitrobenzoic acid (3). For these esters, the catalytic activity of 4 at pH 〉9 was found to be in the following order: 3 〉 2 〉 1 that for 1 being a retarding one. Copolymer 5 shows a reverse catalytic activity of the order 1 〉 2 〉 3. The catalytic site of the alternating copolymer 4 is the free imidazolyl group, and the reaction rate is enhanced by the carboxylate anion, whereas the reaction rate in the presence of the random copolymer 5 is controlled predominantly by electrostatic interaction forces between the substrate and sequential carboxylate anions.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021841009
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    Electronic Resource
    Electronic Resource
    Orientation of ketones embedded in a polyethylene matrix. Infrared dichroic studyDedicated to the 70th birthday of Prof. O. Wichterle (1983)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 2075-2080 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Low-molecular weight ketones embedded in polyethylene films were oriented by cold drawing of the films and the effect of temperature on the orientation was studied by IR dichroism. The loss of orientation of the low-molecular weight ketones with temperature is discussed on the basis of the Cohen-Turnbull model of “free volumes”.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1983.021841012
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