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  • 1
  • 2
    Publication Date: 1980-01-01
    Print ISSN: 0301-0104
    Electronic ISSN: 1873-4421
    Topics: Chemistry and Pharmacology , Physics
    Published by Elsevier
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  • 3
    Publication Date: 1990-01-01
    Print ISSN: 0003-2670
    Electronic ISSN: 1873-4324
    Topics: Chemistry and Pharmacology
    Published by Elsevier
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Theory and Simulations 7 (1998), S. 407-419 
    ISSN: 1022-1344
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: New models for the steric environment of Ti isospecific polymerization sites for poly(propylene) on MgCl2 microcrystals are proposed. They directly involve a donor molecule in order to obtain isospecific activable Ti atoms otherwise belonging to isolated adsorbed TiCl4 molecules or Ti2Cl8 dimers which are lacking of the required chirality for stereocontrol. The donor molecules able to attain at best this effect keep to some peculiar conformational rules settled by the authors in a previous theoretical-correlative study on highly active Lewis bases. The new 1,3-dimethoxypropane series suggested by the authors and recently patented by Montell has been examined in detail. Essentially three different types of closeness between Ti atoms and donor molecules can take place, in which different moieties of the diether compound help to build the ‘right’ steric environment in the site's neighbouring. In the three proposed models S1, S2, S3 the stereocontrol is attained through, respectively, one of the methoxy moieties, one of the methyls, and one of the central carbon atom substituents. New hypotheses on the role of Lewis bases in the preparation of isospecific heterogeneous Ziegler-Natta catalysts are discussed.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Theory and Simulations 7 (1998), S. 399-405 
    ISSN: 1022-1344
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A correlative approach is illustrated in which some conformational features of Lewis bases used in Ziegler-Natta heterogeneous catalysts for isotactic poly(propylene) proved to be molecular descriptors strongly correlating with stereoregulating power and polymerization yield. They are both steric and statistical descriptors and have been obtained through the analysis of the entire rotational hypersurface of the considered compounds. The correlative study selected some of their values as necessary conditions for a good stereoregulating effect. Their calculation for new molecules led to the predictive evaluation of new chemical classes as efficient stereoregulating electron donors and to the choice of the most effective ones.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Poly(1-methylhexamethylen) (1a), Poly(1-methyloctamethylen) (1b), Poly(1-methyldecamethylen) (1c) und Poly(1-methyldodecamethylen) (1d) wurden mittels Röntgenweitwinkel legung untersucht. Diese Polymeren zeigen eine partielle intra- und intermolekulare Didnung und können als äthylen/Propen-Copolymere betrachtet werden, die längs der lette regelmäßige Sequenzen von 2,3,4 und 5 äthylenbausteinen je Propylenbaustein uthalten.Die Unregelmäßigkeit der Konfiguration der tertiären Kohlenstoffatome hat gezeigt, daß die Polymeren ataktisch sind. In den geordneten Bereichen nehmen die Gerüstketten Zick-zack-Konformationen ein. Die Packung der Makromoleküle wird durch die seitenständigen Methylgruppen bedingt, deren Einfluß von 1d nach 1a zunimmt.Eine intermolekulare „Fernordnung“ wurde für die Gerüstketten beobachtet, während für die seitenständigen Methylgruppen nur eine intermolekulare „Nahordnung“ zu finden ist. Die Strukturen. die für diese Polymeren vorgeschlagen werden, scheinen auch für statistische Äthylen/Propen-Copolymere mit ähnlicher Zusammensetzung zu gelten.Auch die Hoch- und Tieftemperatur-Strukturen von alternierenden Propen/Butadien-Copolymeren werden beschrieben.
    Notes: Poly(1-methylhexamethylene) (1a), poly(1-methyloctamethylene) (1b), poly(1-methyldecamethylene) (1c), and poly(1-methyldodecamethylene) (1d) were studied by high-angle X-ray diffraction methods. The polymers reveal a partial intramolecular and intermolecular order and may be considered as ethylene/propene copolymers containing, along the chains, regular sequences of 2,3,4, and 5 ethylene units every propylene unit, respectively.Configurational disorder at the tertiary carbon atoms was evidenced so that the polymers are atactic. In the ordered regions, the backbone chains assume planar zig-zag conformations. The packing of the macromolecules is conditioned by the side methyl groups, and their influence increases going from 1d to 1a.An intermolecular “long range order” was evidenced for the backbone chains, while + an intermolecular “short range order” is present for the methyl side groups. The structures proposed for these polymers seem to be possible also for ethylene/propene +dom copolymers having similar compositions.The low and high-temperature structures of propene/butadiene alternating copolymers are also described.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die hoch schmelzenden und am leichtesten kristallisierenden Produkte der Isomerenmischungen, die bei der additiven Chlorierung von 1,5-Hexadien bzw. cis,cis-2,6-Octadien erhalten wurden, erwiesen sich bei der Röntgenbeugungs-Analyse als meso-Stereoisomere, und zwar (RS)-1,2,5,6-Tetrachlorhexan (TCH) bzw. (RRSS)-2,3,6,7-Tetrachloroctan (TCO).Die Kohlenstoffatome liegen in beiden Strukturen als fast planare Zick-zack-Ketten vor, mit den Chlor-Atomen in gauche-Stellung bezüglich der Kohlenstoffatome. Diese Strukturen werden mit denen der kristallinen Kettenabschnitte von entsprechend chlorier-ten cis- und trans-Poly( 1 -alkenylenen) verglichen. Die Kristalle von TCH sind monoklin, haben die Raumgruppe P21/n und Z=2 in der Elementarzelle mit den Dimensionen: a=9,02±0,03; b=10,09±0,03; c=5,23±0,02Å; β= 100°12′±20′. Die Kristalle von TCO sind monoklin, haben die Raumgruppe P21/n und Z = 2 in der Elementarzelle mit den Dimensionen: a=10,97±0,03; b=8,66plusmn;0,02; c=6,27±0,02 Å; β = 101° 55′ ± 20′. Die Röntgenanalyse ist mit einer Stoeö-automatisierten Weissenberg-Kamera durchgeführt worden. Die Strukturbestimmung mit Hilfe der Technik der kleinsten Quadrate ist im Fall von TCH für 1076 Reflexe bis zu R=0,06 und im Fall von TCO für 973 Reflexe bis zu R =0,078 verfeinert worden.
    Notes: The high melting and most easily crystallizable products of the isomer mixtures obtained by addition chlorination of 1,5-hexadiene and cis,cis-2,6-octadiene were found, by X-ray analysis, to be the meso stereoisomers (RS)-1,2,5,6-tetrachlorohexane (TCH) and (RRSS)-2,3,6,7-tetrachlorooctane (threo-disyndiotactic structure) (TCO) respectively.The carbon atoms in both structures are in a nearly planar zigzag, while the side chlorine atoms are in a gauche position in respect of the carbon atoms. These molecular structures are compared with those of the crystalline chain segments obtained by addition chlorination of cis and trans poly(1-alkenylenes). The crystals of TCH are monoclinic, space group P21/n, with Z=2 in a unit cell having dimensions: a=9,02±0,03, b=10,09±0,03, c=5,23±0,02 Å β=100°12′±20′.The crystals of TCO are monoclinic, space group P21/n, with Z=2, in a unit cell of dimensions: a=10,97±0,03, b=8,66±0,02, c=6,27±0,02 Å, β=101°55′±20′. The X-ray analysis has been performed with a Stoë-automated Weissenberg camera. The structures have been refined by least-square techniques to R=0,06 for 1076 reflections in the case of TCH and R=0,078 for 973 reflections in the case of TCO.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular and crystal structure of 1,4-bis(chloroacetyl)-trans-2,5-dimethylpiperazine synthesized by us, was determined from X-ray diffractometer data. The structure was solved by Patterson and Fourier methods and refined by least-squares techniques to R 0,065 for 1081 independent reflections. The crystals are monoclinic, space group P21/n, with Z = 2 in a unit cell of dimensions: a = 9,486 (6), b = 9,139 (6), c = 7,036 (5) Å, β = 95,73 (10)°, the numbers in parentheses being the estimated standard deviations refering to the last significant digit. The trans-2,5-dimethylpiperazine ring is in a flattened-chair conformation with the side methyl groups in axial position. The atoms of the amide are nearly coplanar. It seems to be proved that the structure of the trans-2,5-dimethylpiperazine ring in poly(trans-2,5-dimethyl-1,4-piperazinediylfumaroyl) is similar to that found for 1,4-bis(chloroacetyl)-trans-2,5-dimethylpiperazine.
    Additional Material: 3 Ill.
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