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  • Articles  (1,763)
  • Articles: DFG German National Licenses  (1,763)
  • Chemistry  (1,763)
  • 2015-2019
  • 1980-1984  (1,763)
  • 1981  (1,763)
  • Physics  (1,763)
  • 1
    Electronic Resource
    Electronic Resource
    Synthesis of polydienes of controlled tacticity with new catalytic systems (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 4 (1981), S. 61-72 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The stereospecific polymerization of diolefins using new catalytic systems based on less conventional transition metal complexes is reviewed. In particular, two families of catalysts based on new complexes of π-allyl type of actinide and lanthanide elements, as well as three component systems formed by rare-earth metal alkoxides, aluminum alkyls, and a Lewis acid are described. A peculiarity of both actinide and lanthanide catalysts is their ability to give, at very low concentration, extremely high cis diolefin polymers and copolymers in aliphatic solvents.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.020041981105
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  • 2
    Electronic Resource
    Electronic Resource
    Recent advances in NMR techniques for the study of synthetic polymers (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 4 (1981), S. 117-127 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The value to polymer chemistry of certain recent developments in NMR is discussed. The techniques in question are: (i) high-field operation, (ii) multinuclear studies, and (iii) the dipolar decoupling/cross-polarization/magic angle rotation experiments on solids. Examples of polymer spectra obtained by these methods are given.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.020041981109
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  • 3
    Electronic Resource
    Electronic Resource
    The structure of polyconjugated macromolecules (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 4 (1981), S. 155-175 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Recent experimental results concerning the crystal structure and morphology of nascent cis-poly-acetylene and pristine trans-polyacetylene are discussed. The unit cell data of cis-PA and two different modifications of trans-PA are reported. The chlorination and the hydrogenation of PA both of which give soluble derivatives under certain experimental circumstances are critically discussed. PA prepared by the Shirakawa technique has a lamellar morphology with some evidence for chain folding and not a fibirillar texture as sometimes assumed. The synthesis and spectral properties of polyenylanions and -cations are reported as a new class of polyconjugated macromolecules. The so-called doping of PA to produce highly conducting phases is explained as a chemical reaction giving rise to intermolecular CT-interaction.Finally, some new experiments concerning the solution properties of polydiacetylenes and the question of effective conjugation length in polyunsaturated polymers are discussed.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.020041981112
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  • 4
    Electronic Resource
    Electronic Resource
    Infrared dichroism, molecular structure, and deformation mechanisms of isotactic polypropylene (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 4 (1981), S. 241-270 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Infrared dichroism measurements can be used to study the process-structure-property relations of a polymer provided the transition-moment angle and phase absorption characteristics of the individual absorption frequencies are known. The present study describes experimental procedures for determining these intrinsic frequency characteristics using isotactic polypropylene as the semicrystalline polymer example. The study further demonstrates the use of this intrinsic information for characterizing the process-structure-property behavior of deformed isotactic polypropylene films. This reveals remarkable similarities in the observed structural response of isotactic polypropylene to different deformation processes.
    Additional Material: 32 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.020041981117
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  • 5
    Electronic Resource
    Electronic Resource
    Stereoregular bioresorbable polyesters for orthopaedic surgeryLectured by Dr Michel Vert, Maitre de Recherche at the French CNRS. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 5 (1981), S. 30-41 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The feasability of using poly(α-hydroxy-acid)s (poly-(glycolic acid), poly(L-lactic acid), L and D-lactic acid stereocopolymers and copolymers of glycolic and L- and D-lactic acids) for processing bioresorbable bone plates, screws, nails etc..., is questioned in regard to the requirements for effective applications and to the data reported in the open literature. Experiments carried out on home-made samples confirm the biocompatibility of these polyesters and the fast resorption of the amorphous compounds. In contrast, our results concerning crystalline poly(L-lactic acid) disagree with those of the literature. The discrepancies might result from differences in the basic material, differences in crystallinity and/or degradation of macromolecules which has been shown to occur sometimes during the elaboration of ready-for-implantation samples. Indeed, quasi-biostable bone plates based on isotactic poly(L-lactic acid) have been obtained according to an elaboration process which preserves the integrity of the synthesized macromolecules. The effects of enantiomeric purity and of implantation time on the tensile strength are reported for a series of welldefined stereocopolymers. Current studies show that highly isotactic poly(lactic acid)s (L/L+D 〉 92%) are polymers of particular interest for effective applications in bone surgery, especially for the construction of completely resorbable composite devices whose reinforcement consists of poly(glycolic acid) fibers.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.020051981103
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  • 6
    Electronic Resource
    Electronic Resource
    Photochemical and spectroscopic behavior of some liquid-crystal polymer systems (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 5 (1981), S. 58-69 
    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, characterization, and applications of liquid-crystalline polymers are emerging areas of scientific research. Lyotropic and thermotropic mesomorphic polymers are briefly reviewed, and the spectroscopic properties of solutes in liquid-crystal polymer hosts are discussed. The results of some photochemical investigations in ordered systems are described. Potential uses of liquid-crystal polymers are given.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.020051981105
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  • 7
    Electronic Resource
    Electronic Resource
    Polymeric catalysts: A contribution to improve the ecology of chemical processes (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 5 (1981), S. 155-178 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymeric catalysts can typically be considered as being a polymeric carrier, to which a catalytically active species - well known in homogeneous catalysis - has been attached in an appropriate fashion. This heterogenization of homogeneous catalysis is of increasing importance due to certain advantages with respect to the ecology of industrial chemical processes. It is the intention of this contribution to discuss two approaches thus illustrating the general statement more specifically. Approach one is the application of ion exchange resins, generally in their protonated form, to perform acid catalyzed reactions in a solid matrix. Approach two is the immobilization of whole, living microbial cells to be applied in heterogeneous biocatalysis.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.020051981110
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  • 8
    Electronic Resource
    Electronic Resource
    Role of structure in transport across membranes (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 5 (1981), S. 179-202 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Interactions between water and two polymers used in membrane technology which are cellulose acetate (39.8% acetyl content: CA) and poly-trans-2, 5-dimethyl piperazinthiofurazanamide (DMP-TFZ) are presented. Experimental adsorption isotherms are discussed on the basis of BET, Zimn, Flory-Huggins theories. DMP-TFZ shows a lower water cluster formation tendency than CA at low and mean activities. The state of water was studied also by IR: in both the polymers the adsorbed water stretching OH frequencies are shifted to higher values showing weaker H bonds than in water. This can be related to the existence of water in the state of monomer and small size aggregates and favours high mobility. The structure of CA dense films is amorphous to X rays, but a certain amount of crystallinity is revealed by DTA. DMP-TFZ is amorphous to X rays, has a high T and shows high stiffness to mechanical dynamical tests. The suggestion is made that stiff chain polymers which contain hydrophilic groups and which cannot easily crystallize, but can get a close packing, do not allow the formation of big free volume packets across which large size water clusters, able to solvate ions, can move.
    Additional Material: 21 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.020051981111
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  • 9
    Electronic Resource
    Electronic Resource
    Studies of static and dynamic aspects of spatial protein structures by high resolution nuclear magnetic resonance spectroscopy (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 5 (1981), S. 234-252 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The potential of high resolution nuclear magnetic resonance (NMR) for many-parameter characterization of biopolymer conformation has long been recognized. Currently new NMR techniques for use in this field are in full development. In the present paper a survey of fundamental aspects of NMR studies of protein conformation is used as a basis for discussion of recently developed one-dimensional and two-dimensional NMR experiments for studies of proteins.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.020051981115
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  • 10
    Electronic Resource
    Electronic Resource
    Polymeric onium salts as catalysts in preparative organic chemistry (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 5 (1981), S. 82-106 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ammonium and phosphonium quaternary salts immobilized on organic and inorganic polymeric matrices are reviewed in relation to their main catalytic applications in preparative organic chemistry. Attention is paid to the systems active in heterophase anion-promoted reactions recognizable in the modern breakthrough created in conventional organic chemistry by the chapter of “phase-transfer” catalysis for its multivalent practical potential. After a mention of early applications in synthetic chemistry performed in the presence of conventional anion-exchange resins, examples of the reports that started to appear in the literature since 1975 on the specific topic of the title have been presented. In particular a rationalization of the specific catalytic activity in phase-transfer reactions has been attempted in terms of the structural parameters directly related to the polymeric matrix. This should not be considered only as a merely inert carrier because of its potential of affecting the specific rate of the overall process under the chemical and stereochemical point of view and defining its morphological and chemical integrity.
    Additional Material: 14 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.020051981107
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  • 11
    Electronic Resource
    Electronic Resource
    Ion-chelating polymers carrying macrocyclic ligands (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 5 (1981), S. 203-215 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ion-chelating properties of linear and network polymers with crown ether and cryptand-type macroheterocyclic ligands either in the backbone or as pendent groups are described. Some of the materials have potential application in trace solute analysis, the removal of radioactive isotopes, separation of ions, the enrichment of isotopes, anion-activated catalysis in organic synthesis and other areas. The properties of the ligand-anchored polymers often differ from those of the monomeric ligands as a result of cooperative effects involving neighboring ligands or other chain substituents.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.020051981112
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  • 12
    Electronic Resource
    Electronic Resource
    The stereoselective and stereoelective polymerizations of some oxiranes (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 5 (1981), S. 230-233 
    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 stereoregulation in polymerization reaction is discussed in terms of the two model cases: (i) the growing chain control mechanism, and (ii) catalyst control mechanism. These two mechanisms were observed to be operated in the stereoselective polymerizations of methyloxirane and of tert-butyloxirane.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.020051981114
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  • 13
    Electronic Resource
    Electronic Resource
    Kinetics of alkaline hydrolysis of polyacrylamide in solution by viscosimetric techniqueNCL Communication No. 2455. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1-8 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The alkaline hydrolysis of polyacrylamide in solution is studied viscosimetrically. The viscosity of the solution increases continuously during the course of hydrolysis. The relationship between intrinsic viscosity and the extent of reaction is established, using a series of polyacrylamides with known extents of hydrolysis. The extent of reaction is determined from the observed flowtime, using the relationship between [η] and extent of reaction. The second-order rate constant and the activation energy are in good agreement with those reported in the literature. A four-fold increased reactivity of the amide groups towards hydrolysis is observed at very low extents of hydrolysis.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820101
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  • 14
    Electronic Resource
    Electronic Resource
    Redox polymerisation, 5.Part 4: cf.8. Kinetics of the polymerisation of acrylonitrile and methyl methacrylate initiated by the system cyanoacetic acid-Mn(III)(acac)3 in DMF and DMSO (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 23-28 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymerisation of acrylonitrile and methyl methacrylate initiated by the system cyanoacetic acid-Mn(III)(acac)3 is investigated in DMF and in DMSO at 25-35°C. Kinetics of reduction of the complex by cyanoacetic acid shows the formation of a mixed ligand complex whose decomposition yields the primary radicals. Efficient initiation of polymerisation by these radicals followed by exclusive mutual termination accounts for the kinetics of polymerisation. Rate and equilibrium parameters are evaluated and their significance discussed.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820104
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  • 15
    Electronic Resource
    Electronic Resource
    Lineare polybenzyle, 6.5. Mitteilung: vgl. J. Skura, R. W. Lenz, Polym. Bull. 2, 31 (1980). Polymerisation von α-methylbenzylchlorid (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 47-58 
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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: α-Methylbenzylchloride (1) was polymerized in ethyl chloride and in 1-nitropropane at various temperatures with AlCl3 as catalyst, mainly at -115 and at 0°C. The polymers obtained were crystalline or amorphous, depending on the reaction conditions. The reactions were complete within seconds. The tacticity of the polymers was determined by 1H and 13C NMR-spectroscopy. Polymers prepared at low temperatures in ethyl chloride showed isotactic sequences; in 1-nitropropane at 0°C atactic configuration. A reaction mechanism for the formation of the isotactic polymer is proposed on the basis of GPC-data. DSC-data are reported and discussed.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820107
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  • 16
    Electronic Resource
    Electronic Resource
    Aromatic spiro polymers (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 59-70 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Aromatic spiro polymers, polyoxoindoline-spiro-benzimidazolines 9a-c, were prepared by the solution polycondensation reaction of biisatyls with aromatic tetramines in polar organic solvents. The spiro polymers were found to exhibit good solubility in polar organic solvents, such as N,N-dimethylacetamide and hexamethylphosphoramide, in contrast to the insolubility of the corresponding polyindoloquinoxalines in these solvents. The improvement of the solubility was discussed mainly in terms of the hydrogen bonding and packing in polymer molecules. The spiro polymers slowly rearranged at high temperatures to give polyindoloquinoxalines with high thermal stability.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820108
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  • 17
    Electronic Resource
    Electronic Resource
    Synthesis and photochemical behavior of polynuclear dithiolato-metal-dye complexesDedicated to Prof. Dr. Georg Manecke of the Free University of Berlin for his 65th birthday (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 105-112 
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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: Polynuclear dithiolato-metal-dye complexes were prepared and their photochemical behaviors were studied. The dimercapto ligands used were maleonitriledithiol (MNT) and toluene-3,4-dithiol (TDT); metal ions were copper, manganese and nickel; and dyes were thionine (TH), tolusafranine (SAF) and methylene blue (MB). From IR spectra, elemental analyses and magnetic measurements they were found to be polynuclear complexes having bis(dithiolato)-metal structure incorporating the dyes as cations. The complexes showed almost the same visible spectra as the free dyes. The molar absorption coefficients of the maximum absorption were in most cases larger than in the free dye. The dithiolato-metal complex affected remarkably the photochemical reactivity of the dye incorporated in it. The rates of the photochemical reduction of the TH complexes (Cu-MNT-TH, Mn-MNT-TH and Cu-TDT-TH) in hexamethylphosphortriamide were higher than the free TH, while those of the SAF complexes (Cu-MNT-SAF and Mn-MNT-SAF) and MB complexes (Cu-MNT-MB and Ni-MNT-MB) were much lower than the free SAF and MB, respectively.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820113
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  • 18
    Electronic Resource
    Electronic Resource
    Immobilisierung von polymergebundenen oligodesoxyribocytidylsäuren an DEAE-celluloseFür die Nomenklatur der Nucleinsäurefragmente werden die Regeln der IUPAC Eur. J. Biochem. 15, 203 (1970) verwendet. TPS steht als Abkürzung für 2,4,6-Triisopropylbenzolsulfonsärechlorid, PVAL für Polyvinylalkohol, TEAB für Triethylammonium-hydrogencarbonatpuffer, DEAE-Cellulose für Diethylaminoethyl-Cellulose, QAE-Sephadex für Diethyl-(2-hydroxypropyl)-aminoethyl-cellulose, Tris für α,α,α-Tris(hydroxymethyl)-methylamin, HMPT für Hexamethylphosphorsäuretriamid. 1A260-Einheit ist die Menge bei 260 nm absorbierenden Materials, die, gelöst in 1 ml, eine Absorption von 1 hat. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 119-131 
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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: N-Anisoyl-deoxyribocytidine-5′-phosphate is chemically polycondensed. From the polycondensate, oligomers containing four or more monomeric units are isolated chromatographically and subsequently linked to a soluble polyvinylalcohol. After cleavage of the nucleobaseprotecting groups, the unreacted oligodesoxyribocytidylic acids are separated from polyvinylalcohol bound oligomers through ultrafiltration. DEAE-Cellulose is subsequently coated with this polymer-bound oligodeoxyribocytidylic acids. The now obtained PVAL-p(dC)n-DEAE-Cellulose acts as a specific sorbent in template-chromatography.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820115
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  • 19
    Electronic Resource
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    Investigation of the electrical conductivity of the iodine-polyphenylacetylene charge-transfer complex (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 165-176 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The electrical conductivity of the charge transfer complex between iodine and polyphenylacetylene (PPA) has been studied. The room temperature d-c conductivity (σ) increased by seven orders of magnitude with iodine addition, reaching a maximum of 10-5 Ω-1 · cm-1 for a 1:1 ratio of iodine to repeating unit, and its concentration dependence could be described by: σ = σ0 exp [γc(1-c) - γ/4], where c is the mole fraction of iodine. Both crystalline and amorphous cis-PPA followed this form, the crystalline polymer having a lower conductivity at low iodine levels, but attaining the same maximum value. The trans-polymer iodinated much less readily than cis-PPA. Molecular weight variations did not influence iodine uptake or conductivity in the range studied. It was possible to remove virtually all iodine from the charge-transfer complex in dynamic vacuum, and an iodine diffusion coefficient of D ≈ 10-11 cm2.s-1 was determined from the rate of weight loss. Passage of current resulted in the evolution of iodine and iodine compounds at the anode. The experiment is consistent with a predominantly ionic conduction mechanism, in which the strong concentration dependence of σ is associated with a concentration-dependent activation energy for ionic charge-carrier formation.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820118
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  • 20
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    Polymerization of 1,3-cycloheptadiene and the structure of poly(1,3-cycloheptadiene)s obtained by ionic initiators (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 215-217 
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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
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820123
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  • 21
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    The colour reaction between poly(vinyl alcohol) and iodine-iodide in the presence of orthotelluric acid (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 225-229 
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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
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820125
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  • 22
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    Studies on carboxymethylcellulose: Potentiometric titrations, 3 (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 243-245 
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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
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820128
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  • 23
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    A new structure for polystyrene-polybutadiene block copolymers: A smectic E type structure (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 265-268 
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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
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820132
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  • 24
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    A new convenient method for the synthesis of poly(styrenesulfonic acid) (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 279-281 
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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
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    Controlled release of fluoride ions from methacryloyl fluoride  -  methyl methacrylate copolymers, 1. Synthesis of methacryloyl fluoride  -  methacrylate copolymers (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 273-277 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 26
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    Syntheses of polymeric cobalt dinitrogen complexes and reduction of the coordinated nitrogen (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 283-291 
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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: Polymeric cobalt dinitrogen complexes were synthesized by two different methods: by the ligand substitution reaction of polymers 5a - c and 6a - c, containing 4-diphenylphosphinophenylethylene units (3) or 4-diphenylphosphinomethylphenylethylene units (4), respectively, with hydridodinitrogentris(triphenylphosphine)cobalt(I) (CoH(N2)(PPh3)3), or by the direct reaction of tris(acetylacetonato)cobalt(III) with triphenylphosphine, the polymers 5a - c or 6a - c, and triisobutylaluminium under nitrogen. The intensity of the vN2 band in the IR spectrum of the polymeric dinitrogen complex was found to be about four times as that of CoH(N2)(PPh3)3. Ammonia was formed after hydrolysis of the complex, which was prepared by mixing a tetrahydrofuran solution of naphthaline, lithium, and titanium tetrachloride with the polymeric dinitrogen complex. The yields of ammonia in the case of the polymeric complexes were high in comparison with that obtained with CoH(N2)(PPh3)3. The highest yields of ammonia were obtained when a mole ratio [P̄]/[Co] 〈 1 ([P̄] is the concentration of phosphino groups in the polymer and [Co] is that of Co in CoH(N2)(PPh3)3), a temperature of -20°C, and a reaction time of 1 h were applied.
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  • 27
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    Synthesis and conformational study of poly(L-valyl-L-valyl-∊-N-benzyloxycarbonyl-L-lysine) in the solid state and in solution (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 549-557 
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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: High molecular weight poly(L-valyl-L-valyl-∊-N-benzyloxycarbonyl-L-lysine) (PVVZL) (7) was obtained by condensation in dimethyl sulfoxide of the L-valyl-L-valyl-∊-N-benzyloxycarbonyl-L-lysine p-nitrophenyl ester, synthesized by the DCCStandard abbreviations for amino acid derivatives and peptides are used according to the I.U.P.A.C.-I.U.B. Commission on Biochemical Nomenclature, Biochemistry 11, 1726 (1972). The abbreviations used are: Boc = tert-butyloxycarbonyl; Z = benzyloxycarbonyl; OBzl = benzyl ester; H-Val-OH = valine; H-Lys-OH = lysine; HONp = para-nitrophenol; DDC = dicyclohexylcarbodiimide; DMSO = dimethyl sulfoxide; TFA = trifluoroacetic acid; TFE = 2,2,2-trifluoroethanol; CD = circular dichroism; IR = infrared spectra. method. The conformation of 7 was studied in the solid state and in solution of 2,2,2-trifluoroethanol, acetonitrile-trifluoroethanol and dioxane-trifluoroethanol mixtures by X-ray diffraction method, CD and IR spectroscopy. The results obtained in the solid state suggest the presence of β-structure, whereas in trifluoroethanol solution, at least, a mixture of random coil and β conformation, probably occurs. The aging of the solution seems to give rise to a higher content of β-structure. The addition of acetonitrile and dioxane favours the formation of an increasing amount of β-structure. Therefore, the conformational behaviour of 7 is similar to that of other sequential polypeptides containing valyl residues, which seem to promote the β-structure.
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    Small angle neutron scattering of molten n-alkane/polyethylene mixturesPresented at the Hamburg Macromolecular Symposium, September 16 - 18, 1980. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 583-587 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820225
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  • 29
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    Spinodale Entmischung von Defekten in Nadelkristallen aus isotaktischem PolypropylenVorgetragen auf dem Hamburger Makromolekularen Symposium 16. - 18. September 1980. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 613-619 
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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
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820229
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  • 30
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    Herstellen von Hochmodulfäden aus PolyethylenVorgetragen auf dem Hamburger Makromolekularen Symposium 16. - 18. September 1980. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 637-642 
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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
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820232
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  • 31
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    The configurational characteristics of conventional poly(methyl methacrylate) in acetonitrile (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 445-449 
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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 θ-temperature and viscosity constant K0 of radically initiated poly(methyl methacrylate) in acetonitrile were determined from the intrinsic viscosity data (θ = 28°C, K0 = 4,3 · 102 g-3/2 · mol1/2.cm3). The unperturbed coil dimensions are lower in acetonitrile than in other θ-solvents at comparable temperature and indicate a more compact conformation of poly(methyl methacrylate) molecules. The discrepancies in the reported data of the θ and K0 values are elucidated.
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  • 32
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    Messungen zum Aggregationsverhalten perfluorierter AlkansäurenHerrn Prof. Dr. M. Seefelder/BASF zum 60. Geburtstag (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 451-481 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: With the use of various techniques an attempt was made to characterize the aggregates that exist in micellar surfactant solutions of salts of the perfluornonanoic acid. The cmc values of the investigated systems were determined by conductivity and surface tension measurements. Conclusions about the shape of the micellar aggregates were drawn from rheologic and electric birefringence measurements. For the lithium, the ammonium and the tetramethylammonium surfactants the existence of normal micelles with spherical shape and with all surfactant ions lying at the micellar surface was found. The perfluornonanoate surfactants with the ammonium counterions that are partially substituted by alkyl groups showed in all investigations a behaviour that was different from the normal case. It was postulated that these solutions contain emulsion-droplet-like giant micelles with the surfactant ions and counterions solubilized as ion pairs in the interior of the micelles. Some of these giant micelles do not have spherical shape; these solutions showed electric birefringence. In most cases the giant micelles disappeared at higher temperatures. Only normal small micelles with spherical symmetry could then be detected and the measured values were again in the range for values of normal C8-perfluordetergents. On the basis of the investigated systems reasons and models for the formation of giant micelles are discussed.
    Additional Material: 11 Ill.
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  • 33
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    Application of electrostatic persistence length to polyelectrolyte solutions (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 559-568 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of added simple salt and polyion charge on the chain flexibility of an alternating copolymer of isobutyl vinyl ether and maleic acid are analyzed. The persistence length of this polymer in aqueous NaCl solution is calculated from sedimentation and viscosity data on the basis of a worm-like chain model. It is found that this polymer is in the state of a highly expanded conformation at low ionic strength, exhibiting a semi-rigid macromolecular behaviour and that it behaves like a rather coiled polymer with small persistence length at high salt concentration. The electrostatic persistence length calculated from the theory of Fixman et al. shows a \documentclass{article}\pagestyle{empty}\begin{document}$ 1/\sqrt {C_{\rm s} } $\end{document}-dependence on added salt concentration Cs.
    Additional Material: 3 Ill.
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  • 34
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    Effect of adjacent functional groups on the electron-donor-acceptor complex formation of diethyl 2,2-bis(dinitrobenzyl)malonates and 2,2-bis(4-dimethylaminobenzyl)malonate (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 739-748 
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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 order to study the effect of adjacent functional groups on electron-donor acceptor (EDA) complex formation, the following donor or acceptor compounds were synthesized: diethyl 2-(2,4-dinitrobenzyl)malonate (13), diethyl 2,2-bis(2,4-dinitrobenzyl)malonate (14), diethyl 2-(3,5-dinitrobenzyl)malonate (5), diethyl 2,2-bis(3,5-dinitrobenzyl)malonate (6), diethyl 2-(4-dimethylaminobenzyl)malonate (10), diethyl 2,2-bis(4-dimethylaminobenzyl)malonate (11). The acceptor compounds 5, 6, 13, and 14 were complexed with N,N-dimethyl-4-dimethylaminoaniline (1) as donor, and the donor compounds 10 and 11, with 1,3,5-trinitrobenzene (2) as acceptor. The wave length of the absorption maximum (λmax), the association constant (KCT), the enthalpy (δH), and entropy (δS) of these EDA complexes were determined. It was found that λmax of complexes 6-1 and 11-2 show a bathochromic shift compared with complexes 5-1 and 10-2, and the values of KCT, -δH, and -δS are higher. The value of λmax for complex 14-1 is not different from that of complex 13-1, and the values of KCT, -δH, and -δS are lower. It was concluded that the stability of the EDA complexes of the 2,2-dibenzylmalonate derivatives 6, 11, and 14, is influenced by π-electron interaction between the adjacent two benzene rings.
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    Préparation d'adsorbants chromatographiques plurifonctionnels et asymétriques. Application à la purification de la céphalosporine C (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 763-771 
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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: Some asymmetric and polyfunctional stationary phases were prepared by attachment of the ε-amino group of L-lysine copper complex to crosslinked polystyrene or agarose, substituted or not by hydrophilic spacer arms. After copper elimination, the sorbents exhibit three functions, one of a carboxylic acid and one of an α-primary amine, and moreover one of a secondary amine located at a variable distance far from the asymmetric carbon, but near the backbone of polymer. These sorbents were tested in the chromatographic extraction of cephalosporin C (1) from an aqueous mixture containing several α-amino acids. They exhibit an affinity higher for the antibiotic than for the amino acids and even for the dicarboxylic amino acids.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820307
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    Synthesis and electrical properties of monomeric and polymeric iron-phthalocyanines (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 811-816 
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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 set of experimental conditions are described for the synthesis of monomeric and polymeric iron-phthalocyanines and compared with those reported in the literature. The dielectric constant and resistivity of characterised samples are studied as a function of temperature. The data indicate possible transitions at 90 and 180°C for monomeric iron-phthalocyanine whereas polymeric iron-phthalocyanine shows no breaks.
    Additional Material: 2 Ill.
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    Graft copolymerization of methyl methacrylate on chlorinated natural rubber, 1. Initiation by various organometallic complexes (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 843-851 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Metallic compounds able to abstract chlorine atoms are investigated for initiating the graft copolymerization of methyl methacrylate on chlorinated natural rubber. An improved method for the separation of the side homopolymer from the graft copolymer is described. The cumulative results demonstrate the greater graft efficiency of the new initiating systems than of the usual free radical initiators.
    Additional Material: 2 Ill.
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    Katalysatoren beim thermischen Abbau von Polymeren, 1. Über den katalytischen Abbau von Polypivalolacton (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 867-871 
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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 ability of different metal oxides and acetates to catalyze the thermal degradation of poly(pivalolactone) into cyclic oligomers has been investigated. Magnesium oxide was found to be the most active catalyst which converts poly(pivalolactone) completely into oligomers within less than two hours at 547 K. The influence of temperature and catalyst concentration and the distribution of cyclic oligomers is discussed.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820318
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    Overall and individual effects in systems including organolithium compounds (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 911-915 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental and quantum chemical data are used for the problem of the relative rǒle of individual factors considering the overall effects which are characteristic of certain Licontaining systems. Recourse is made to the following processes: polymerization of isoprene in the presence of subcatalytic amounts of electron donors; polymerization of acrylonitrile by RLi and ROLi initiators; polymerization of dienes by butyllithium (n-BuLi) and tert-butyllithium (tert-BuLi).
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/macp.1981.021820321
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  • 40
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    Adiabatic polymerization of ε-caprolactam in presence of lithium chloride, 1. Thermodynamic and Kinetic aspects (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 929-939 
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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 activated anionic polymerization of ε-caprolactam in presence of LiCl (up to 10 wt.-%) is studied under quasi-adiabatic conditions. The temperature increase of the system, after proper corrections for the heat exchange with the surroundings, allows to evaluate the enthalpies of polymerization δHp and to correlate their variations with the specific interactions of LiCl with monomer and polymer. The sharp decrease of -δHp as function of LiCl content is attributed to the stabilizing effect of the ion-dipole interactions, which is higher for the monomer-salt pair than for the polymer-salt mixture. The initial rates of polymerization are enhanced by a few percents of added LiCl, with a maximum at about 3 wt.-%. The relative influence of various physical factors on the polymerization kinetics and thermodynamics is discussed.
    Additional Material: 6 Ill.
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    Polymerization of tetrahydrofuran by bifunctional cationic initiators: Terephthaloyl perchlorate (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 731-737 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics and mechanism of the polymerization of tetrahydrofuran with terephthaloyl perchlorate in methylene chloride or cyclohexane were analyzed. This polymerization produces dicationically active polymers and takes place without induction period. Propagation in both solvents proceeds as a reaction being first order in monomer, and it changes with the polarity of the solvent because ionic and covalent species take part with different growing rates. The macroester mole fractions in cyclohexane and methylene chloride are 0,99 and 0,86, respectively.
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    Recherche de télomères à activité pharmacologique potentielle, 2Partie 1: cf.25.. Télomères de l'acide acrylique et greffage de composés hydroxylés (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 773-784 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several telomers of acrylic acid with carbone tetrachloride were prepared. Their average degree of polymerization, which was between 10 and 50, was determined by several analytical methods (elemental analysis, viscosimetry, and GPC). From the kinetic equations of telomerization a relation between DPn of these telomers and the experimental conditions is established. Fixation of hydroxylic compounds through direct esterification was studied and it was found that the prepared telomers can be used as hydrosoluble carriers for drugs containing primary alcohol or phenol functions.
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    Polymers containing enzymatically degradable bonds, 1. Chymotrypsin catalyzed hydrolysis of p-nitroanilides of phenylalanine and tyrosine attached to side-chains of copolymers of N-(2-hydroxypropyl)methacrylamidePresented at the 25th IUPAC Symposium on Macromolecules, Mainz, FRG, September 1979. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 799-809 
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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 copolymers of N-(2-hydroxypropyl)methacrylamide were prepared, which contained side chains of the general formula -Gly-X-Y-NAp, where Gly ¨ glycine; X ¨ glycine, alanine, β-alanine, valine, leucine, isoleucine, phenylalanine; Y ¨ phenylalanine or tyrosine; NAp ¨ p-nitroanilide, the latter modelling biologically active compounds. The rates of chymotrypsin-catalyzed hydrolysis of p-nitroanilide groups at pH = 8,0 and 25°C were determined over a range of substrate concentrations to derive values for kcat and KM. The results allowed us to determine the influence of the structure of side chains on the rate of cleavage of Y-NAp. The increase in the susceptibility to chymotrypsin attack with an increasing spacing of the Y-NAp residue from the backbone of the polymer chains is demonstrated by comparing the kinetic data of copolymers containing -Gly-Gly-Phe-Phe-NAp, -Gly-Gly-Phe-NAp and -Gly-Phe-NAp side chains. Results obtained with α-chymotrypsin were compared with the cleavage of the above polymer substrates with chymotrypsin covalently bound to a copolymer of N-(2-hydroxypropyl)methacrylamide.
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    Synthesis and properties of aromatic polypyrazoles from bis(β-substituted vinyl ketones) and aromatic dihydrazines (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 837-842 
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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: Polycyclocondensations of aromatic dihydrazines 2a and 2b with 1,6-diethoxy-1,5-hexadiene-3,4-dione (1a) in m-cresol and those with bis(3-chloroacryloyl)benzenes 1b and 1c in 1-methyl-2-pyrrolidone (NMP) lead to aromatic polypyrazoles 3a - f having inherent viscosities up to 0,35 dl.g-1. The polymers are soluble in polar aprotic solvents like NMP and some acidic media including m-cresol. Thermogravimetry shows a loss of 10 wt.-% at ≈ 500°C both in air and nitrogen.
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    Synthesis of polyamides containing 4,4′-azodibenzamido unitsPaper presented at the International symposium on“New Frontiers in Polymer Science and Polymer Applications”, held at Madras (1980). (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 853-859 
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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 coloured polyamides containing azo-p-phenylene units were synthesised from 4,4′-azodibenzoic acid and four aromatic diamines employing both interfacial and solution polymerization procedures. The polymers were characterized by their UV and IR spectra, by inherent viscosity measurements and by solubility data. The stability in conc. sulfuric acid and the thermal behaviour are discussed.
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    Caractérisation texturale de résines en milieu réactionnel (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 873-882 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoporometry, a method based on the microcalorimetric analysis of liquid-solid state transformation inside porous substances, gives access to porous volume versus pore size distribution. For the first time, this method is applied to the analysis of flexible products swellable in the reference medium. Conditions for applying transposition thermoporometry to this new class of porous substances are discussed. An example is given, which leads to suggest a model for the swelling process of a macroporous resin. Generalization of this method would induce a major progress in the study of swollen systems and enable better understanding of their structures.
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    Subkatalytische Effekte in Systemen Isopren/Organolithium/Elektronendonator, 3Teil 2: cf1.. System Isopren/Oligoisoprenyllithium/1,2-Dimethoxyethan (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 917-920 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular weights and structural characteristics of the polymers formed in the system isoprene/oligoisoprenyllithium (OILi)/1,2-dimethoxyethane (DME)/hexane (mole ratio DME/OILi = 0,01) for various conversions at -30°C were determined. The results obtained corroborate the former conclusion that the complexation of an electron donor with the monomeric form of the growing chain reduces the reactivity of the latter.
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    Polymethacrylic acid Derivatives, 1. Preparation, Characterization, and Potentiometric study of poly(N-methacryloyl-L-alanine-co-N-phenylmethacrylamide) (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 949-963 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(N-methacryloyl-L-alanine) and poly(N-methacryloyl-L-alanine-co-N-phenylmethacrylamide) containing up to 38 mole-% of N-phenylmethacrylamide were synthesized by radical copolymerization. These polymers were characterized by UV and IR spectroscopy and by conductimetric titrations. The samples were then studied by potentiometric titrations in pure water and in aqueous organic solvents, in the temperature range of 5 - 65°C. The experimental results show that, opposite to poly(methacrylic acid), poly(N-methacryloyl-L-alanine) takes no compact structure in water. The insertion of N-phenylmethacrylamide induces the appearance of this compact structure over 15 mole-% of this residue. Thereafter, the stability of the compact structure increases when increasing the amount of N-phenylmethacrylamide. Experimental results suggest that it is due to increasing Van der Waals interactions between the hydrophobic side chains.
    Additional Material: 11 Ill.
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    Lamellar crystalline structure of block copolymers with an amorphous and a crystallizable block: Effect of the nature of the crystallizable block (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 989-995 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Block copolymers of styrene and ethylene oxide (SEO) and of styrene and ε-caprolactone (SCL), in the dry state and in the presence of a preferential solvent of the amorphous block, exhibit a lamellar crystalline structure at temperatures below ≈50°C. In this structure the crystallized chains are folded in two superposed layers. To investigate the effect of the nature of the crystallizable block, two copolymers SEO and SCL of the same relative molecular mass and composition were studied by X-ray diffraction and differential scanning calorimetry. It is established that the nature of the crystallizable block influences the crystallinity and the number of folds of the crystallized chains and the swelling of the amorphous polystyrene block.
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    Versuche zur umsetzung von methylendiphenolen mit glucosederivaten und zur kondensation von O-phenylglucosidderivatenHerrn Prof. Dr. Gustav Stählin, Universität Mainz, zum 80. Geburtstag gewidmet. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1351-1361 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Attempts to apply known methods of glucosidation to oligo[(hydroxyphenylene)methylene]s were not satisfying. The reaction of 4,4'-dimethyl-2,2'-methylenediphenol (1a) with 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide gave a monoglucoside in 11% yield. A second attempt, the condensation of suitable O-phenylglucoside derivatives was unsuccessful. From a series of O-phenylglucosides (4) only 4-(2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyloxy)benzylbromide could be condensed with O-(4-hydroxymethylphenyl)-2,3,4,6-tetra-O-acetylglucopyranose to the corresponding diglucoside of 4,4'-oxydimethylenediphenol (7). Condensation reactions of the O-phenylglucoside 4k, to obtain an O-glucosidized poly[(hydroxyphenylene)methylene], were accompanied by decomposition. The results showed that the usual methods of the preparation of glucosidized phenols cannot be transferred to oligomeric or polymeric derivatives.
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    The anionic polymerization of 2-pyrrolidone in bulk and in suspension (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1399-1405 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: A study on the anionic polymerization of 2-pyrrolidone in bulk and suspension under isothermal conditions is described. After a discussion about the disadvantages of the bulk process carried out by using N-potassium-2-pyrrolidone as initiator and N-acetyl-ε-caprolactam as activator, a possible alternative way is proposed on the basis of the suspension polymerization initiated by N-potassium-2-pyrrolidone and activated by silicon tetrachloride. The ultraviolet absorption spectra of the polymer samples obtained by the above methods reveal that undesiderable side reactions leading to degradation of the keto amide groups, are almost negligible under the aforementioned conditions.
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    Changes of molecular weights of thermally exposed polymers (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1441-1447 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Theoretical relations between the change of molecular weights of thermally exposed polymers with arbitrary initial distribution and time have been derived. These relations were used to correlate the changes of molecular weights of thermally exposed polypropylene.
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    Solid phase photoreduction of methylviologen on cellulose (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1111-1118 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Methylviologen (1,1′-dimethyl-4,4′-bipyridinium dichloride, MV2+) absorbed on cellulose paper can be reduced photochemically in solid phase. The ESR spectrum (singlet; g = 1,967, ΔHmsl = 13,5 gauss) shows the photochemical formation of its cation radical (MV•+). The MV•+ formed on cellulose is unusually stable against oxidation by oxygen. Photochemical formation and slow oxidation of MV•+ under air occur fairly reversibly. The concentration of MV•+ and the optical density (O.D.) at 620 nm show a linear relationship. The concentration of MV•+ at 1 O.D. corresponds to 1,07.10-8 spins/cm2 cellulose paper. The formation of carbonyl groups in MV2+/cellulose after irradiation indicates that cellulose acts as electron donor. The mechanism of the solid phase photoreduction is discussed in relation to the effect of other carbohydrates or inorganic materials as adsorbents.
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    A theoretical study on the 1H NMR chemical shift of alanine oligopeptides (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1097-1109 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: All the NH and α-CH proton chemical shifts of alanine oligopeptides (Ac-(Ala)n-NHMe, where n = 1-6) with extended and α-helical conformations and anti-parallel β pleated-sheet structure, were calculated by taking into account the magnetic anistropy effect due to the C=O and two kinds of C—N bond anisotropies, and the electric-field effect. The observed spectral behavior of the NH or CH protons in Ac-Ala-NHMe and Ac-(Ala)2-NHMe could be mostly predicted from the calculation, which indicates that the NH and CH chemical shifts in these oligomers are mainly determined by the intramolecular shielding effect. On the other hand, the appearance of the “doublet α-CH peak” for oligomers with chain lengths of five or more reported by Goodman et al. could not be interpreted in terms of the intramolecular shielding effect. In this case, therefore, whether the CH protons are shielded from the solvent or not, seems to be a dominant factor for the origin of the “doublet peak”. The magnetic anisotropy effect of a peptide group was also examined.
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    Polybutadiènes hydroxytéléchéliques, 4.Partie 3: Cr. Fages, Q.-T. Pham, Makromol. Chem. 180, 2435 (1979). Microstructure des polybutadiènes hydroxytéléchéliques radicalaires observée par 1H NMR à 350 MHz et mécanismes de propagation (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1167-1176 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The examination by 1H NMR spectroscopy at 350 MHz of commerical hydroxytelechelic polybutadienes Arco R45M® allows the quantitative determination of the in-chain vinylcentered triads and the 4 types of hydroxylated vinyl chain ends. Vinyl primary radicals as well as macroradicals were found to propagate with penultimate and pen-penultimate effects.
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    Polymérisation anionique de l'acroléine, 2.Partie 1: cf.1. Influence de la nature du contre-ion et de la température sur la cinétique de la réactionTexte de la communication présentée à l'IUPAC de Mainz, septembre 1979. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1215-1227 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: In tetrahydrofuran, with Na+ and Li+ as counter-ions, the kinetic order of the anionic polymerization of acrolein is unity for monomer and for initiator. These results indicate that the living ends are not associated at the studied concentrations of initiator. The polymerization rate depends on the nature of the counter-ion. Transfer reactions to monomer do not affect the polymerization rate but greatly change the molecular weights Mn of polyacroleins. The experimental M are much lower than the theoretical M. The propagation constants kpr and the transfer constant hm are determined using these experimental values of M. From these results, we can conclude that with Li+ as counter ion, transfer reactions are much more numerous than with Na+. Furthermore, the polymerization rate increases with temperature. The activation energies of the propagation (Ea,pr) and transfer reactions (Ea,t) can be determined separately. When the temperature increases the propagation reaction is promoted in comparison to the transfer reaction to monomer, and simultaneously transfer reactions to polymer take place. This last phenomenon restricts the upper value of the polymerization temperature.
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    Oxydation photocatalytique des polypropylènes isotactique et atactique (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1229-1241 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: By photooxidation of isotactic and atactic polypropylene (PP), irradiated at wavelengths 〉300 nm in air, alcoholic, acidic, ester, lactonic, and unsaturated functions are formed as shown by IR spectrophotometry. The primarily formed hydroperoxy and ketone groups are rapidly photolyzed and their concentrations are kept low. In presence of UV absorbing pigments like TiO2 or ZnO, the same photoproducts are formed with lower rates than in the transparent polymers. In atactic PP, ZnO and TiO2 (rutile or anatase) show different photoactivities. When the light is absorbed in ZnO, accumulation of ketone and lactonic groups is observed. When TiO2 is the absorbing species, oxidation is going further and acidic, ester, and lactonic functions may be observed; TiO2 appears to be able to photocatalyze the disappearance of ketone groups. In isotactic PP of high cristallinity, direct photooxidation and photocatalyzed oxidation are superimposed and differences between ZnO and TiO2 cannot be observed.
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    Effect of solvent on 13C NMR chemical shifts of tetrad methylene carbons of poly(vinyl chloride) (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1243-1251 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The 13C NMR chemical shifts of tetrad CH2 carbons of poly(vinyl chloride) are observed in solvents covering a wide range of relative dielectric constants and show extreme sensitivity to the solvent. The chemical shifts are interpreted theoretically by means of the solvaton-CNDO/2 MO theory.
    Additional Material: 3 Ill.
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    Synthesis and tumor-inhibiting activity of new heparin-bound nitrogen mustard analogues (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1679-1683 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: New nitrogen mustard analogues in which bis(2-chloroethyl)-amino groups are separated by oxyethylene groups, 1,14-dichloro-3,12-bis(2-chloroethyl)-3,12-diaza-6,9-dioxatetradecan (3c) and 1,17-dichloro-3,15-bis(2-chloroethyl)-3,15-diaza-6,9,12-trioxaheptadecane (3d), were synthesized by reaction of bis(2-hydroxyethyl)amine (2) with bis(2-chloroethyoxy)ethylene (1a) and with 1,11-dichloro-3,6,9-trioxaundecane (1b), respectively, followed by treatment with thionyl chloride. The analogues were then complexed with heparin. The resulting heparin-complexes show inhibiting activity against transplanted Sarcoma-180 A in mice.
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    Cosolvents of PMMABased on a Communication presented to the IUPAC International Symposium on Macromolecules, Florence (Italy), September 7 - 12, 1980. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1705-1714 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Several cosolvent mixtures for PMMA are reported. Their cosolvency has been confirmed by studying phase separation temperatures as a function of solvent composition. The results show that they are very powerful cosolvents. Acetonitrile forms such cosolvent mixtures with compounds containing different chemical groups (ester, ketone, alcohol, chloroalkane). The mixtures of acetonitrile with alcohols are nonsymmetrical with respect to the solubility parameter value of PMMA. They cannot be explained by simple δ theory. The mixture of formamide with ethanol is also nonsymmetrical and constitutes a true cosolvent pair for PMMA. The associating tendency of the polymer in the single solvent, plus the somewhat ordered structure of the pure liquids, are invoked to suggest that cosolvency is attained by breaking such order and association (in addition to the existence of unfavourable interactions between the cosolvents).
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    Ion-trapping in cationic polymerization, 2.Part 1: cf.1. Relative rates of trapping and relative chemical shifts for structurally differing phosphines as trapping agentsPresented in part at the IUPAC Macromolecular Symposium in Mainz, September 1979. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1735-1742 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The reaction of ethyl trifluoromethanesulfonate with phosphines to form phosphonium salts was used as a model reaction for the “trapping” of the various propagating species by phosphines in the polymerization of THF and other cyclic ethers. In dichloromethane at 25°C, the values of the bimolecular rate constant ktr were determined for various phosphines. For (C6H5)3P:5.10-3 mol-1.l.s-1, for (C6H5)(CH3)2P:0,22 mol-1.l.s-1, for (C6H5)(n-C3H7)-(CH3)P:0,13 mol-1.l.s-1, and for (n-C4H9)3P: 1,3 mol-1.l.s-1. It was found that the ratio ktr/ka (ka is the rate constant of the ethylation of THF by ethyl trifluoromethanesulfonate) changes from 40 for triphenylphosphine to 104 for tributylphosphine. Differences of chemical shifts, measured for various quaternary phosphonium cations differing in one substituent, were observed for ions with various substituents (e.g. based on parent methylpropylphenylphosphine).
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    Einfluß des temperns auf die negative thermische ausdehnung von polyethylen (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1787-1799 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The linear thermal coefficient of expansion for high density polyethylene, extended to draw ratios λ = 8 to 16 is α = -24·10-6 K-1 at 20°C. This value results from the orientation of crystallites with an expansion coefficient αc = -12·10-6 K-1 and from stresses in the amorphous phase. Using the model of series coupling of crystalline and amorphous parts the value αam ≤ -50·10-6 K-1 is calculated for a crystallinity xv = 70%. From measurements of Young's modulus the fraction of tie-molecules χtie = 0,4% of the sample is assessed and the expansion coefficient αtie = -90·10-6 K-1. Annealing of the samples leads to shrinkage while the density ρ increases slightly and the expansion coefficient α increases considerably. Samples annealed at temperatures closely below the melting point show a slight decrease of the density at 20°C but a value of α exceeding that of isotropic samples. This effect can be explained by preferred orientation of the crystal a-axis in fibre direction as soon as orientation starts to break down.
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    Long-term change in conformation of macromolecules in solution, 2.Part 1: cf.1. Poly(acrylamide-co-sodium acrylate)sPaper in part presented at the International Symposium on Macromolecules (IUPAC), Florence (Italy) on Sept. 7 - 12th (1980). (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2277-2287 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The solution viscosity of aqueous poly(acrylamide-co-sodiumacrylate)s decreases with time in the scale of weeks. This unusual viscosity loss has been investigated by viscometry and by light scattering on high purity copolymer samples with different ratios of the components.  -  No viscosity loss can be observed in NaCl solution of high enough salt concentration. From the experiments it is concluded that a conformational change causes the viscosity decrease. No chain scission occurs. Light scattering measurements were used to directly confirm this hypothesis.  -  The viscosity loss may be caused by a conformational change of single molecules involving hydrogen bonds and can be interpreted as a transition from a partly stiffer, higher viscous structure to a more flexible one. As the driving force for the conformational change the entropy is discussed. The pronounced time dependence may be interpreted by a cooperative effect of loosening and combining of hydrogen bonds.  -  A similar behaviour has been observed earlier in aqueous poly(acrylamide) solutions. Thus, for some water soluble polymers one has to be aware of a time dependent parameter.
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    Carbon-13 relaxation study of crosslinked gels of poly(methyl methacrylate) (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2289-2295 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The motion of covalently crosslinked gels of poly(methyl methacrylate) (PMMA) swollen by benzene-d6 was studied by means of 13C NMR spectroscopy. The dependence of the segmental motion of PMMA on stereosequence was not affected by the presence of the covalently crosslinked part in the chain; isotactic sequence was more mobile than syndiotactic sequence. The spin-lattice relaxation times, T1's, for all the 13C nuclei of PMMA swollen with benzene (benzene content, 90 wt.-%, 0,01 mole-% of crosslinking) were considerably longer than those observed for the linear PMMA (benzene content, 75 wt.-%). Moreover, all the T1 values decreased with increasing of the degree of crosslinking, regardless of the crosslinking agent and reached to the values of T1 observed for uncrosslinked PMMA or to slightly larger values when the content of crosslinking agent was 1 mole-%. However, the nuclear Overhauser enhancement data were essentially independent of the degree of crosslinking within experimental error.
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    Polymérisation anionique de l'acroléine, 3.Partie 2: cf.9. Analyse des microstructures par 1H NMR et 13C NMR et mécanisme de polymérisation (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2321-2342 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: We have synthesized anionic polyacroleins using various initiators (naphthalene complex, tert-butyllithium) in different solvents (tetrahydrofuran, toluene). We have studied the 1H NMR and 13C NMR spectra of the polymers and assigned monomeric units and diads by comparison with spectra of four compounds corresponding to the different microstructure arrangements. By this method, we have clearly proved the presence of 1,4- as well as 3,4- and 1,2-units. But numerous cyclisations occur on the 1,2-units. Using only the 1H NMR method, a first estimation of the microstructure was obtained. 13C NMR gave further information and permitted the estimation of the (1,4-cis)/(1,4-trans) ratio. Furthermore the presence of hydroxyl groups along the chains has also been established. A satisfactory determination of the 1,2,3,4- and 1,4-structure percentages of several polyacroleins has been obtained using 1H NMR and 13C NMR simultaneously. A mechanism of acrolein polymerization, based on two different living ends is proposed. The microstructure indicates the existence of several complexation phenomena. When the living end/metal and monomer/metal complexations are weak (with Na+ e.g.), the polymer consists mainly of 1,4- and 3,4-units. On the other hand, with Li+, the microstructure has a high 1,2-content. Moreover, the living end/Li+ complexation would decrease with the chain length, because of the increasing attraction of the cation by the other complexing sites on this chain.
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    Linear oligopeptides, 78.Part 77: cf.1. The effect of the insertion of the proline residue on the solution conformation of host peptides (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2007-2014 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformational properties of three series of monodispersed, chemically and optically pure, PEGThe following abbreviations have been used in the text: PEG, poly(ethylene glycol); -NHPEG, “amino-PEG”; -NHPEG-M, “amino-PEG” -monomethyl ether; t-Boc, tert-butyloxycarbonyl; Z, benzyloxycarbonyl; Ala, alanine; Met, methionine; Gly, glycine; Glu, glutamic acid; Pro, proline; OBzl, benzyloxy; OEt, ethoxy; CD, circular dichroism; MeOH, methanol; TFE, 2,2,2-trifluoroethanol; HFIP, 1,1,1,3,3,3-hexafluoro-2-propanol.-bound linear host oligopeptides of the general formula \documentclass{article}\pagestyle{empty}\begin{document}$ t{\rm - Boc\rlap{--} (L - Met\rlap{--} )}_n {\rm NHPEG} $\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ t{\rm - Boc\rlap{--} (L - X\rlap{--} )}_n {\rm NHPEG - M} $\end{document} [X = Ala, Glu(OBzl)] containing a single guest L-Pro residue at different positions in the main chain have been investigated in aqueous and alcoholic solutions as a function of concentration, temperature, and added salts using CD. The corresponding N-deblocked peptides have also been examined. The incorporation of the L-Pro residue into a host petide chain blocks the extension of the α-helical conformation at the level of the segment containing the guest residue at its N-terminal end. The investigations reveal asymmetric helixnucleation properties of the L-Pro residue as predicted by theory. In β-structure-forming oligopeptides, the insertion of a L-Pro residue results in a significant destabilization of the ordered conformation. Thus, aggregation of peptide chains is less pronounced in these co-oligopeptides.
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    Styrene-divinylbenzene copolymers, 3.Part 2: cf H. Jacobelli, M. Bartholin, A. Guyot, Angew. Makromol. Chem. 80, 31 (1979). Revisited IR analysisThis work is part of a research project. (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2075-2085 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A critical analysis of the styrene-divinylbenzene resin infra-red spectra was made using previous works and new results. A method for the determination of pendent double bonds and also crosslinking degree and composition of the resin is drawn. A few examples of application are given.
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  • 68
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    Eine neue methode zur ermittlung kinetischer und kalorischer daten einer radikalischen copolymerisation durch differentialthermoanalyse (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2095-2103 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The heats of copolymerization of styrene and methyl methacrylate were measured by means of differential thermal analysis (DTA). Extrapolating the DTA curves to time zero, monomer reactivities and the ratio of the rate constants of termination can be obtained by a new method of evaluation. Calibration is not necessary for this procedure. With calibration, however, the rates and the heats of polymerization can also be measured. The data agree well with those reported in the literature.
    Additional Material: 4 Ill.
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  • 69
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    A novel synthetic route to all-ortho novolac resins (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2151-2159 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A facile synthesis of ortho-linked novolacs was achieved by reaction of selected metal phenolates with paraformaldehyde. Both solvent and phenolate counter-ion play a leading role in the ortho-specific methylene-bridging of the phenolic nuclei. The combined use of highperformance liquid chromatography and 13C NMR spectroscopy proved to be successful in the characterization of these resins.
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  • 70
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    Succinic half-esters of poly(ethylene glycol)s and their benzotriazole and imidazole derivatives as oligomeric drug-binding matrices (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2183-2192 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: α-Hydroxysuccinyl-ω-hydroxysuccinyloxypoly(oxyethylene)s (succinic half-esters of poly-(ethylene glycol)s) (2) of different molecular weights were prepared, and transformed into the corresponding benzotriazole and imidazole derivatives 3 and 4. The benzotriazolyl or the imidazolyl residues in these polymers can easily be exchanged. This was proved with model compounds bearing hydroxyl or amino groups. Polymers of this type may be considered as potential oligomeric drug-binding matrices.
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  • 71
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    Temperature effect on the stereoelective polymerization of methylthiirane in homogeneous phase (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2225-2231 
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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: Chiral cadmium thiolates of cysteine with cyclohexyl or (-)menthyl ester groups were prepared and compared with similar compounds (with isopropyl or methyl ester groups) as initiators for stereospecific polymerization of methylthiirane in homogeneous phase. The resulting polymers are highly isotactic and in all cases stereoelection can be reversed with a small change in polymerization temperature. This temperature effect permitted to differentiate two stages in the polymerization corresponding to the formation of a precursor and to that of a high polymer, respectively.
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  • 72
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    Asymmetric-selective polymerization of (R,S)-α-methylbenzyl acrylate initiated with Grignard reagent/(--)-sparteine and its modified systems (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2737-2746 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Asymmetric-selective (or stereoelective) polymerization of racemic α-methylbenzyl acrylate (2a) was studied with Grignard reagent/(-)-sparteine and its modified catalyst system in toluene. All catalyst svstems polymerized preferentially the (R)-monomer over the (S)-monomer. The Grignard reagent/(-)-sparteine system showed very low activity and gave the polymer only in a few per cent yield at -78°C. The addition of secondary amines such as piperidine and diethylamine to the catalyst system improved not only the activity but also the selectivity. The optical purity of the polymer initially formed with the cyclohexylmagnesium bromide/(-)-sparteine/diethylamine system at - 78°C was 84%, and at about 80% polymer yield almost optically pure monomer was recovered. Asymmetric selectivity decreased with an increase of temperature. The dyad tacticity of the polymer was determined by 1H NMR spectroscopy. There was no clear correlation between the selectivity and tacticity. The role of the amines in the catalyst systems was investigated by 1H NMR spectroscopy.
    Additional Material: 4 Ill.
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  • 73
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    Flow properties of ethylene/vinyl acetate copolymers (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2789-2800 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of linear and branched fractions of an ethylene/vinyl acetate (EVA) copolymer is characterized by viscometry and gel permeation chromatography (GPC) exclusively. Characterization results are applied to the study of the influence of branching on flow properties of concentrated solutions of EVA fractions. Newtonian viscosity-concentration-molecular weight relationships are obtained for both linear and branched samples. Graessley's theory of entanglements for linear polymers is tested with a set of fractions. Experimental flow curves come out to be independent of the linear or branched nature of the samples.
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  • 74
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    The effect of monomer crystal structure on the solid-state polymerization of N-vinylcarbazole (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2351-2357 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The solid-state polymerization of N-vinylcarbazole initiated by γ-rays was studied by X-rays, IR and GPC techniques to understand the role of the monomer crystal structure on the polymerization mechanism. From the X-ray diffraction results it was possible to explain the chain growth mechanism and limiting conversion. The molecular weight distribution and the role of oxygen was explained from the GPC results. Liquid chromatography and IR results were used to explain the nature of unpolymerized monomer after reaching the limiting conversion. It was proved that the unpolymerized monomer retains its crystal structure and does not react to any other compounds.
    Additional Material: 5 Ill.
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    Oxidative polymerization of 2,6-bis(3-methyl-2-butenyl)phenolDedicated to Professor, Dr. Georg Manecke on his 65th birthday (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2361-2369 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Oxidative polymerization of 2,6-bis(3-methyl-2-butenyl)phenol (1) was carried out by copperpyridine catalyst. 1 was oxidatively polymerized to yield poly[oxy-2,6-bis(3-methyl-2-butenyl)-1,4-phenylene] (2) in a similar manner as it has been observed for 2,6-dimethylphenol (3a). 2 is an oily material with a degree of polymerization of 6,2. 1 and 3a copolymerized with similar reactivity to form the copolymer 4 (degree of polymerization 16 to 29). The 3-methyl-2-butenyl groups in the polymer show enough chemical reactivity for an addition of bromine or graft-polymerization.
    Additional Material: 5 Ill.
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    Untersuchung der grignard-wurtz-reaktion von partiell hydrobromiertem 1,4-polybutadien und partiell α-bromiertem polyoctenylen durch metathese-abbau der polymere und identifizierung der niedermolekularen produkteHerrn Prof. Dr. Dr. h. c. F. Patat zum 75. Geburtstag gewidmet (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3041-3052 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Partially hydrobrominated 1,4-polybutadiene and α-brominated polyoctenylene were treated with pentyl, isopropyl, cyclohexyl, benzyl, 4-methylbenzyl, phenyl, 4-methylphenyl, 4-ethylphenyl, 3,4-dimethylphenyl, 2,4,6-trimethylphenyl, 4-chlorophenyl, 4-fluorophenyl, 4-methoxyphenyl, 3,4-dimethoxyphenyl, and 2-thienyl magnesium bromide. In addition partially hydrobrominated 1,4-polybutadiene was treated with 2-methylbenzyl, 3-methylbenzyl and 4-isopropylphenyl magnesium bromide. Polymers were degraded by metathesis with 4-octene using WCl6/(CH3)4Sn as a catalyst. The low molecular products were separated by gas chromatography and identified by mass spectrometry. Mass spectra of products with 4-alkyl(aryl)octanediylidene units (from modified polybutadiene) and 2-alkyl(aryl)octanediylidene units (from polyoctenylene) were compared.
    Additional Material: 6 Ill.
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    13C NMR sequence analysis, 20Part 19: H. R. Kricheldorf, H. Sekiguchi, B. Coutin, J. Polym. Sci., Polym. Chem. Ed. submitted.. Stereospecificity of the polymerization of D,L-Leu-NCA and D,L-Val-NCAN-Carboxyanhydrides (Oxazolidine-2,5-diones). (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3077-3098 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The copolymerization of D- and L-Leu-NCA as well as that of D- and L-Val-NCA was studied under various conditions. Even nonpolar solvents, such as diethyl ether or ligroin, used for the precipitation of the poly(D,L-amino acid)s, were found to have an influence on yield and tacticity of the isolated polypeptides indicating that atactic polypeptides of low molecular weight may be soluble in these solvents. 13C NMR spectra of the isolated poly(D,L-amino acid)s were measured in trifluoroacetic acid and the carbonyl signals were used for the evaluation of the teacticity. Under all reaction conditions only a moderate degree of stereospecificity was found. D,L-Leu-NCA initiation with protic nucleophiles, such as benzylamine or diethylamine, favors the formation of isotactic blocks. In the case of D,L-Val-NCA again isotactic blocks are slightly favored if benzylamine is used as initiator, while diethylamine, like other strong bases, causes preferred formation of syndiotactic sequences. With strong aprotic bases and electrophilic cocatalysts, i.e. under conditions favoring the “activated monomer mechanism”, the highest degrees of stereospecificity were observed. However, in the case of D,L-Leu-NCA isotactic blocks are predominantly formed, while in the case of D,L-Val-NCA syndiotactic blocks are favoured. Changing the solvent may result in a reversal sense of the stereospecificity. The absence of long isotactic blocks in all samples of this work was also demonstrated by the good solubility of all samples in various organic solvents.
    Additional Material: 4 Ill.
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    Copolymers of 2-acrylamido-2-methylpropanesulfonic acid and aromatic vinyl compounds as potential media for photosensitized electron transfer reactions (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3135-3147 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In an expectation as potential media for photosensitized electron transfer reactions, polymers carrying both strong electrolytic and hydrophobic segments were prepared by the copolymerization of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and styrene. The AMPS segments were found to have a remarkable power to solubilize the hydrophobic segments into water, i.e., even a copolymer with a styrene mole fraction of 0,72 is still soluble in water. Salt effect on the reduced viscosity, broadening of NMR spectra in D2O, and enhanced excimer fluorescence of styryl groups in aqueous solution indicated a pronounced hydrophobic interaction of a number of styryl groups along the chain in the copolymer with high styrene content. 8-Anilinonaphthalene-1-sulfonic acid, 1,6-diphenyl-1,3,5-hexatriene, and a cyanine dye were used as fluorescent probes for the hydrophobic microdomains. The results suggested that the microdomains are highly hydrophobic in nature but less capable to solubilize the fluorescent probes than the surfactant micelles. An electron microscopic image of the copolymer was also discussed as a supporting evidence for the presence of microdomains.
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    Internal mobility of PMMA in concentrated CDCl3 solutions, 1. 1H NMR spectra (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3169-3176 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of the second moment and analysis of the derivative shape of 1H NMR spectra of PMMA have shown that in CDCl3 solutions containing 60% (w/w) or more of polymer, the internal mobility of PMMA is similar to the mobility of the pure polymer. The main chain is rigid on the NMR scale, and only CH3 groups are mobile. The motion of CH2 groups, representing the segmental mobility of the backbone chain, becomes appreciable on the NMR scale at concentreations of 60-50%, depending on the temperature. Measurements of 1H MAR-NMR spectra of solutions containing 30% or more of polymer indicate spatial anisotropy of internal motions of PMMA. This spatial anisotropy is probably due to intermolecular interactions of ester groups, similarly as in the gels of the PMMA stereocomplex.
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    Die molekulargewichtsverteilung bei der kontinuierlichen anionischen polymerisationHerrn Professor Dr. Dres. h. c. G. V. Schulz mit den besten Wünschen zum 75. Geburtstag gewidmet (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3207-3221 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Equations are given for the continuous anionic polymerization in a tubular reactor which describe the resulting molecular weight distribution as a function of the size of the mixing zone and of the concentration of chain terminating impurities in the solution of the monomer. Polymerization of styrene and of butyl methacrylate was conducted with different initiator concentrations, and the size of that part of the reactor where backmixing occurs was estimated from the molecular non-uniformity of the polymers, whereas the degree of polymerization allows the determination of the concentration of the impurity. This latter quantity apparently increases with initiator concentration in the case of methacrylate polymerization and therefore suggests a reaction of the initiator with the ester group to occur. The shape of the molecular weight distribution indicates termination of the growing methacrylate chains, possibly by reaction of living chain ends with ester groups.
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    Elementarprozesse löslicher ziegler-katalysatoren. Polymerisationskinetische analyse und mathematische modellierung im system Cp2TiPropylCl/AlEtCl2/ethylenHerrn Prof. Dr. Dr. h. c. Franz Patat zum 75. Geburtstag in Verehrung gewidmet (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3265-3278 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: This paper deals with the kinetics of the polymerization of ethylene catalysed by the soluble Ziegler-catalyst Cp2TiPropylCl/AlEtCl2. By means of a special method it was possible to study the kinetics of the initial instationary homogeneous part of the polymerization. The dependences of the initial rates on the catalyst components prove that the polymerization active species is formed in two successive very dynamic equilibria. The primary complex equilibrium is entirely located on the right hand side, whereas the second equilibrium depends considerably on the ratio of the catalyst components and is shifted on the active species side only at very high Al/Ti ratios. Because of this location of the two successive equilibria the dependence of the polymerization velocity vp on the charged Al concentration (that is, the Al isotherm) has to show a sigmoidal curve course in the inital part, which experimentally is confirmed exactly. Finally, this extensive kinetical analysis leads to the complete reaction scheme of the polyreaction and by mathematical modelling to the quantitative calculation and description of the experimental curves and dependences (e.g., Al-isotherm).
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    Thermomechanical analysis of linear aromatic polyesters (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3323-3330 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermomechanical properties of linear aromatic polyesters, studied using thermomechanical analysis techniques, have been related to the chemical structure and methylene chain length. An increase in the number of methylene groups, the use of an asymmetric diacid, or random copolymerization of the repeating units of these polyesters, resulted in a lower linear thermal expansion coefficient α, a lower Vicat softening temperature Ts, a lower heat deflection temperature Td, and a lower glass transition temperature Tg. With longer methylene sequence lengths, the influence of the methylene groups on the thermomechanical properties is predominant, the data are closer together. The values are generally highest for the terephthalate series and lowest for the copolymer series. Glass transition temperatures calculated from group contributions and measured experimentally agreed. The deflection temperatures approximated the glass transition temperatures and the Vicat softening points the melting temperatures.
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    Phase distribution chromatography (PDC) as a method for the investigation of polymers in solution, 2Part 1: Cf.1.. Flow-equilibrium (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2845-2861 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamical region of the measured calibration curves is investigated using the results of the theory published previously. The kinetic constants of the flow-equilibrium are calculated from the measurements according to two different models for a spontaneous polymer diffusion of the transported P-mer from sol into gel of the Phase Distribution Chromatography (PDC)-column. The corresponding lateral concentration profiles in the gel are found by analytical integration of Fick's second law under the corresponding boundaries. An energetic model of this flow-equilibrium is stated, giving the activation enthalpy and -entropy of the rediffusion of the polymer from gel into sol after some retardation time in the gel. The influence of the gel mass of the column on its resolution is briefly investigated. Since the measurements show that the resolution of the PDC-column vanishes in the vicinity of the theta point, spreading phenomena in the column can be investigated by means of analysis of the corresponding PDC elution curves. The results give a basis for the numerical computation of the molecular weight distribution of narrowly distributed polystyrenes from PDC elution curves at sufficiently low column temperatures. The PDC-separation effect is opposite to that of gel permeation chromatography (GPC).
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    Lösungseigenschaften methyl- und chlorsubstituierter Bisphenol-A-PolycarbonateHerrn Prof. Dr. Grünewald zum 60. Geburtstag gewidmet (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2873-2879 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solution properties of dilute polymer solutions are studied for polycarbonates from 3,3′,5,5′-tetramethylbisphenol A, from 3,3′-dimethylbisphenol A, from 3,5-dimethylbisphenol A, and from 3,3′,5,5′-tetrachlorobisphenol A in regard to the influences of the different methyl and chloro substitutions. The Mark-Houwink relationships are established in dichloromethane at 25°C. The unperturbed dimensions, evaluated from viscosity data using the Burchard-Stockmayer-Fixman method, are compared with those for bisphenol A polycarbonate. The unperturbed end-to-end distances are increased by the methyl and chloro substituents. The flexibility factors, calculated on the basis of the unperturbed dimensions and the dimensions of the freely rotating chain, indicate a greater rigidity of the polymer chain of the methyl and chloro substituted polycarbonates.
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    Polymers containing enzymatically degradable bonds, 4Part 3: cf.3. Preliminary experiments in vivo (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2941-2949 
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    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Copolymers of N-(2-hydroxypropyl)methacrylamide containing oligopeptidic sequences either in side chains or as part of crosslinks were prepared. These polymers were applied intravenously to rats, and spectrophotometric analysis (oligopeptidic side chains) or gel permeation chromatography of urine (oligopeptidic crosslinks) have shown that both types of polymers are cleavable in vivo.
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  • 86
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    Uncatalysed phenol-formaldehyde reactions. A convenient synthesis of all-ortho novolac resinsCf.:1 (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 2973-2979 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The uncatalysed reaction between phenol and paraformaldehyde in aprotic nonpolar media at 170-220°C provides an efficient inexpensive route to novolac resins with almost all of the methylene-linkages in ortho-ortho′ sequence. The role played by the solvent is shown to be determinant in the ortho-specific insertion of methylene-bridges between the phenolic units.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021821105
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  • 87
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    The structure of poly(N-vinylcarbazole) obtained with cationic initiators and electron acceptors as catalysts (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3003-3015 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(N-vinylcarbazole)s, [poly(l-(N-carbazolyl)ethylene)s], (PVCz's) were prepared under various polymerization conditions. The stereoregularities were estimated by means of 13C NMR spectroscopy. Although the stereoregularity of the polymers obtained by BF3O(C2H5)2 was hardly changed by the polymerization temperature, it changed with the solvent polarity from an isotactic-rich configuration in toluene and CH2Cl2 to a syndiotactic-rich configuration in nitrobenzene. The 13C NMR spectra of the polymers obtained by organic electron acceptors, support the conclusion that the polymerization by tetracyanoethylene, p-bromanil, 2,3-dichloro-5,6-dicyano-p-benzoquinone, and tetrachlorophthalic anhydride proceed by a cationic mechanism. In the polymerization of N-vinylcarbazole (VCz) with maleic anhydride as an electron acceptor, a small amount of copolymer was obtained together with the homopolymer of VCz. Although the structure of the homopolymers is the same as that of the radically obtained polymer, it is considered that the polymer is formed by a cationic mechanism. The polymerizations of VCz by inorganic compounds, such as ferric nitrate, cupric nitrate, cupric bromide, etc., as catalysts are cationic.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021821109
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  • 88
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    Etude de radicaux libres forméas par irradiation ultraviolette de l'amidon: Application aux réctions de photodégradation et de photogreffage (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3053-3068 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: General investigations of radical processes in starch were carried out. ESR experiments showed that UV irradiation of starch, both in photosensitized and unphotosensitized experiments, results in chain scission and radical generation on the glucosidic ring. It was shown that benzophenone, deoxybenzoin and derivatives (2a-d) are efficient sensitizers. The ESR spectra were interpreted by assuming superposition of three signals; they were ascribed to radicals formed by chain scission and hydrogen abstraction. In addition photodegradation processes of starch in the presence and absence of photosensitizers were investigated. The amount of chain scissions was followed under various experimental conditions and appeared as a function of the initiator. Moreover, oxygen was shown to enhance the yield of chain scissions: this was explained through the formation of peroxide functions at C1-position. UV light induced grafting of a vinyl monomer onto starch was also investigated. It appeared that chemical grafting can easily be achieved through a radical reaction. Moreover, the percentages of grafting and degradation were strongly dependent on the photoinitiator. The whole results gave the possibility to select an efficient initiator of the grafting reaction. In the case of methyl methacrylate, α,α-dimethoxydeoxybenzoin (2a) appears to be the most efficient initiator. However, previous works as well as the present work suggest that the grafting efficiency is strongly dependent on the three components: substrate, monomer, and initiator.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021821113
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  • 89
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    Electric dipole moment of ethylcellulose, in 1,4-dioxane and in benzene (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3109-3117 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The electric dipole moments per repeating unit of ethylcellulose (EC) of various molecular weights were determined by dielectric measurements at 1 kHz (μL) and at 1 MHz (apparent moment, μH) in 1,4-dioxane and benzene. The numerical values were μL = 5,23 D (= 17,45.10-30 C·m) and μH + 2,72 D (= 9,07.10-30 C·m) for 1,4-dioxane, and μL = 4,81 D (= 16,04.10-30 C·m) and μH = 2,42 D (= 8,07.10-30 C·m) for benzene, respectively. μL and μH were almost independent of the molecular weight in both solutions. The persistence dipole moment μq was estimated to be 13,6 D (= 45,36.10-30 C·m) in 1,4-dioxane, and 13,4 D (= 44,70.10-30 C·m) in benzene, respectively, and the flexibility of the EC chain was discussed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021821117
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  • 90
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    Hot drawing of surface growth polyethylene fibers, 2Part 1: cf.2. Effect of drawing temperature and elongational viscosity (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 3351-3359 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A distinct improvement of the tensile properties of “surface growth” polyethylene fibers can be realised by drawing at elevated temperatures. The optimal drawing temperatures were found in the range of 120-150°C. Drawing in the hexagonal phase above 150°C does not lead to an increase of strength. Elongational viscosity measurements revealed extremely high values in the order of 1011-1012 Poise. Activation energies between 75-95 kJ/mol were determined from the temperature dependence of elongational viscosity. The observed drawing behaviour is discussed in relation to the morphological changes that occur during drawing.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021821138
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  • 91
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    The synthesis of stereoregular polymers by vinyl, ring-opening, and condensation polymerization reactions (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 4 (1981), S. 47-59 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The important factors which control the stereochemistry of polymerization, and thereby the crystalline properties of the polymers so formed, are considered for four different types of reactions including: (1) the cationic polymerization of substituted α-methylstyrenes to form syndiotactic polymers; (2) the anionic ring-opening polymerization of substituted β-propiolactones to form crystalline polyesters; (3) the metathesis ring-opening polymerization of 1,5-cyclooctadiene to form poly(1,3-butadiene)s of controlled cis-trans contents; and (4) the condensation polymerization of α-methylbenzyl chloride to form isotactic poly(α-methylbenzyl).
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.020041981104
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  • 92
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    Sequence regulation in spontaneous binary and ternary copolymerizations via zwitterion intermediates (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 4 (1981), S. 73-84 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper is concerned with the sequence regulation of monomeric units in a series of binary and ternary copolymerizations which proceed without any added catalyst or initiator. The binary copolymerization is consisted of the combination of a nucleophilic monomer (MN) and an electrophilic monomer (ME). The interaction between the two monomers generates a zwitterion of a 1:1 adduct, which is the key intermediate in the copolymerization producing 1:1 alternating copolymer. The varieties of MN and ME monomers, the structures of key intermediates of zwitterions, and the schema of copolymerizations have been discussed. In addition, the “Sequence-Ordered 1:1:1 Terpolymerization” (producing terpolymers of a type .…ABCABCABC….) and “2:1 Binary Copolymerization” (producing copolymers of a type of .…ABBABBABB….) are described, which have been developed on the basis of the above binary 1:1 alternating copolymerization.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.020041981106
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  • 93
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    Electronic Resource
    Mismatched bases in nucleic acids: their effects on structures and stability (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 4 (1981), S. 143-153 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of ribo- and deoxyribo-oligonucleotides were synthesized with the sequences CAnG, CUmG AND CTmG (n and m = 5 or 6). These molecules can form RNA, DNA and hybrid double stranded helices containing either perfect base pairing (n = m), or mismatches (n ≠ m). The thermodynamics of formation of these helices has been measured and the destabilization caused by an extra uridylic, thymidylic or adenylic residue has been determined. Nuclear magnetic resonance of exchangeable imino protons has been used to study the conformations of the different helices. The binding of ethidium to the helices has been studies.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.020041981111
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  • 94
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    Morphology and viscoelastic properties of isotropic and oriented polypropylene films (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 4 (1981), S. 207-222 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The physical structure of semicrystalline polymers influences many of their properties. It has been shown that thermal treatment (rate of cooling and annealing) as well as the action of mechanical forces (drawing) of isotactic polypropylene (PP) resulted in materials with different mechanical properties. In the case of isotropic films the crystallization temperature or annealing temperature from the glass and consequently morphological structure which has been formed, determine the values of modulae, yield stress and viscoelastic properties. Reoptical behaviour has been found to be sensitive to structural differences too. The structure and mechanical properties of highly oriented PP samples which have been obtained by drawing through a flat die have been found to be dependent on parameters characterizing this process (drawing rate, apex angle of die and elongation ratio).
    Additional Material: 20 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.020041981115
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  • 95
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    Catalytic behaviour of metalcomplexes immobilized in functional polymeric carriers (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 5 (1981), S. 121-154 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The general principles of construction of gel-immobilized catalyst systems (GICS) are reported as well as some peculiarities of the polymerization of ethylene and of the dimerization of ethylene and propylene in the presence of these systems.GICS consist of a transition metal complex and a specially designed polymeric support. Advantages offered by gel-immobilized catalyst systems are discussed with respect to homogeneous and microheterogeneous metal complex catalysts.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.020051981109
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  • 96
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    Electronic Resource
    Polymerization of epoxides catalysed by metalloporphine (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1073-1079 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The catalyst system obtained by the equimolar reaction of diethylaluminium chloride with α,β,γ,δ-tetraphenylporphine exhibits high catalytic activity in the polymerization of propylene oxide to give a polymer with a narrow molecular weight distribution. Average molecular weight of the polymer can be controlled by the initial mole ratio of propylene oxide to catalyst or by the conversion. Ethylene oxide also produces a polymer having a narrow molecular weight distribution.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820408
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  • 97
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    The influence of molecular interaction on polymerization, 5.Part 4: H. Boudevska, C. Brutchkov, V. Veltchev, Eur. Polym. J. 15, 907 (1979). Copolymerization of benzyl methacrylate with maleic anhydride (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1119-1125 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Copolymerization of benzyl methacrylate (BMA) with maleic anhydride (MA), initiated by 2,2′-azoisobutyronitrile at 70°C in chloroform or acetonitrile, were investigated. The complex formation between the two monomers in chloroform was studied by 1H NMR spectroscopy. The stability constant of the complex was found to be 0,25 l.mol-1. The following copolymerization reactivity ratios were found: in chloroform: rBMA = 0,188 ± 0,035 and rMA = 0,003 ± 0,005, in acetonitrile: rBMA = 0,116 ± 0,093 and rMA = 0,231 ± 0,027. By 1H NMR investigations it could be shown that the results correlate with the changes of the reactivity ratios depending on the solvent used.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820412
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  • 98
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    1H and 13C NMR studies on N-acetyl-L-alanyl-L-alanine-methylamide (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1153-1165 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 1H and 13C NMR spectra of N-acetyl-L-alanyl-L-alaninemethylamide and N-acetyl-L-alanyl-L-alanine methyl ester were measured in [2H]6-dimethyl sulfoxide and deuteriochloroform/trifluoroacetic acid solutions. The assignments of the N-terminal and internal NH proton peaks of the amide could be made by means of deuterium exchange experiments in [2H]6-dimethyl sulfoxide solution. An association model of the amide with an antiparallel β-sheet structure was proposed by taking into account the presence of an IR absorption at 1 690 cm-1 as amide I band and the results of the measurement of 3JHN-CαH coupling constants, as well as the deuterium exchange experiment. Moreover, the interaction between the peptide units in these two compounds and trifluoroacetic acid seems to be weaker than the N-acetyl-L-alaninemethylamide-acid interaction in a deuteriochloroform/trifluoroacetic acid solvent system of the same concentration.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820416
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  • 99
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    Copolymères du chlorure de vinylidène avec l'acrylonitrile, le chlorure de vinyle et le méthacrylate de méthyle, 2.Partie 1: cf.4. Fusion  -  utilisation d'un modèle de simulation (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1207-1214 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melting point depression in vinylidene chloride copolymers, when introducing an increasing number of units B = vinyl chloride, acrylonitrile or methyl methacrylate is studied in this paper. A Monte-Carlo simulation model of chains growing and crystallization is applied and allows to know the proportion Xc of defects in the crystalline phase. An equation given by Sanchez is then applied, and the excess energy ε of the defect created by the incorporation of a B unit in the crystalline vinylidene chloride lattice is calculated.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820420
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  • 100
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    Time resolved small angle scattering during isothermal crystallization of unoriented poly(ethylene terephthalate) using synchrotron radiation (1981)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1263-1269 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The time course of the small angle scattering pattern of amorphous poly(ethylene terephthalate), (PET), was measured during isothermal crystallization using synchrotron radiation. The samples were heated to temperatures between 117 and 145°C in an oven placed in the path of the X-ray beam. The scattering curves were measured within 10 s at intervals of 1 s so as to follow the kinetics of the process continuously. It appears that the distance between the centres of mass of the crystallites decreases with increasing crystallization time as in oriented PET. The integrated small angle scattering follows approximately the same time course as the increase in the degree of crystallinity during an isothermal crystallization yielding Avrami exponents between 5 and 7. Guinier plots of the low angle region show that the scattering can be attributed to rod-like particles.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1981.021820425
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