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  • Polymer and Materials Science  (184)
  • Life and Medical Sciences  (76)
  • Physics  (35)
  • 1
    Electronic Resource
    Electronic Resource
    Superactive and stereospecific catalysts. IV. Influence of structure of esters on MgCl2 supported olefin polymerization catalystsPart III of this series: J. C. W. Chien and Y. Hu, J. Polym. Sci. Polym. Chem. Ed., in press. (1990)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 28 (1990), S. 273-284 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: CH-type catalysts were prepared by reacting MgCl2 · ROH, where ROH is 2-ethyl hexanol (EH), (R)-2-octanol (R-20), and (S)-2-octanol (S-20), with TiCl4 in the presence of di-i-butyl phthalate (BP), di-i-butyl terephthalate (BT), (-)-dimenthyl phthalate (MP), or (-)-dimenthyl terephthalate (MT). The MT catalysts were found to incorporate 8.9 to 13% Ti whereas the BP catalysts contain only 1.9 to 2.6% Ti. Comparison of the CH(EH, BP) and CH(EH, MT) catalysts showed that they have about equal number of isospecific active sites per gram of catalyst and the same rate constants of propagation for their nonspecific sites, however, the isospecific sites in the latter are less active by comparison. Consequently, the CH(EH, BP) catalysts is five times more active than the CH(EH, MT) catalysts and produces polypropylene which is 97% isotactic (reflux n-heptane insoluble) as compared to 84.7% for the latter. The catalysts derived from 2-octanols are much less active than the corresponding catalysts prepared with 2-ethyl hexanol due to lack of reactivity with phthalic anhydride which permits excessive incorporation of TiCl4 to form nonstereospecific catalytic sites as well as inactive Ti species.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1990.080280204
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  • 2
    Electronic Resource
    Electronic Resource
    Effect of polarity of the medium on the stereospecific polymerization of propylene by ansa-zirconocene catalyst (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2049-2056 
    Details
    ISSN: 0887-624X
    Keywords: metallocenes ; olefin polymerizations ; Ziegler-Natta catalysts ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Propylene was polymerized with rac-ethylene-bis (1-η5-indenyl)dichlorozirconium/methylaluminoxane in solvents of different polarity. The poly (propylene) formed was separated by solvent extraction; 13C-NMR and DSC measurements were made on the polymer fractions. The poly(propylene) in each solvent fraction has its characteristic molecular weight steric pentad distributions, melting transition temperature, and enthalpy for fusion irrespective of the polymerization medium. The results suggest that the medium dielectric constant does not affect the polymerization rate or the intrinsic stereoselectivity, propagation and chain transfer rates a given catalytic species but can alter the occurrence of steric insertion errors through shifting of distributions of the propagating species producing poly(propylenes) of different stereoregularities. © 1994 John Wiley & Sons, Inc.
    Additional Material: 7 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080321106
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  • 3
    Electronic Resource
    Electronic Resource
    Solid-State NMR characterization of a superactive supported ziegler-natta catalystThis is Part XXXI of the series on MgCl2-supported Ziegler-Natta catalyst. Part XXX was: J. Vizzini, F. Ciardelli, and J. C. W. Chien, “Stereoselective Polymerization of α-Olefins by Heterogeneous Chiral Ziegler-Natta Catalysts,” Macromolecules, 25, 3199 (1992). (1993)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 48 (1993), S. 2173-2179 
    Details
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The formation of CH-type catalysts has been investigated by high-resolution and solid-state NMR. These catalysts are prepared from a soluble MgCl2 and 2-ethyl-1-hexanol adduct (MgCl2·3EH) by reaction with phthalic anhydride (PA) to form dioctylphthalate (DOP) and then with TiCl4 in the presence of di-i-butylphthalate (BP). In the model systems MgCl2·3EH/PA, MgCl2/BP, and MgCl2/TiCl4/BP, the ester is complexed with MgCl2 and /or TiCl4 in two or more states. Only single-ester C=O and OCH2 resonances are seen in TiCl4/BP, probably due to exchange of ester coordinations. CH-catalysts prepared by three different procedures exhibit a single mode of bonding for the ester. The chemical shift values are consistent for ester complexed with MgCl2. The most active and stereoselective catalyst has the most shielded chemical shift values for the C=O and  - OCH2 -  carbons, shortest TH1 and TH1p, and longest TCH relaxation times. These parameters change monotonically with the decrease of activity and stereoselectivity of the catalyst preparation. © 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1993.070481211
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  • 4
    Electronic Resource
    Electronic Resource
    Difference in stereoselective polymerization of 4-methyl-1-hexene by homogeneous and heterogeneous Ziegler-Natta catalysts (1992)
    Basel : Wiley-Blackwell
    Die Makromolekulare Chemie, Rapid Communications 13 (1992), S. 479-484 
    Details
    ISSN: 0173-2803
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/marc.1992.030131101
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  • 5
    Electronic Resource
    Electronic Resource
    Noncomplementarity in base sequences between the cohesive ends of coliphages 186 and λ and the formation of interlocked rings between the two DNA's (1967)
    New York : Wiley-Blackwell
    Biopolymers 5 (1967), S. 953-966 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The half molecules of 186 DNA have been isolated by the Hg(II)-Cs2SO4 density gradient centrifugal ion technique. The buoyant densities of the two halves in CsCI at 25°C. are 1.713 and 1.709 g./cm.3, corresponding to GC contents of 54% and 50%, respectively. Similarly, 5-bromouracil labeled λ DNA halves were separated. The isolation of the four DNA halves made it possible to test for homology in base sequences between the cohesive ends of λ and those of 186. There was no indication of any significant homology in base sequences between the cohesive ends of the two DNA's, as indicated by the absence of a band with intermediate buoyant density in CsCI when either half of 186 DNA was annealed with either half of 5-bromouracil labeled λ DNA and then centrifuged. The lack of cohesion between the two DNA's made it possible to demonstrate unequivocally the formation of interlocked rings (catenanes) between the two DNA's. The existence of a dimeric catenane is evidenced by the formation of a species of intermediate buoyant density when 5-bromouracil labeled λ DNA is cyclized in the presence of cyclic 186 DNA of a relatively high concentration. The molecular weight of one DNA relative to the other can be calculated from the position of the dimeric catenane in a density gradient by using the method of Baldwin. The result was in complete agreement with our previous measurements from the sedimentation coefficients and by electron microscopy. The probability of dimeric catenane formation when one DNA is cyclized in the presence of another DNA is discussed. The experimental results agree with the theoretical expectation.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1967.360051008
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  • 6
    Electronic Resource
    Electronic Resource
    Polymer reactions, 8.Part 7: cf.3. Oxidative pyrolysis of poly(propylene)This work was supported in part by a grant No. G7-9010 from the Center for Fire Research of the National Bureau of Standards. (1980)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 47-57 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(propylene) has been oxidized at temperatures between 240 and 289°C. The products were GC separated and on-line identified by an interfaced GC peak identification system. The major products are CO2, H2O, acetaldehyde, acetone, butanal, formaldehyde, methanol and other ketones and aldehydes. Most of the products can be accounted for by well-known reactions of alkoxyl and peroxyl radicals; the major products are derived from the secondary alkoxy and peroxy species. Oxygen starvation is manifested in diffusion limited products of olefins and dienes, and the increase of CO2 and H2O formation in pure oxygen atmosphere. The first order rate constant at 240°C is 2,4·10-3 S-1 with an overall activation energy of ca. 16 kcal·mol-1 (67 kJ·mol-1). If one assumes the oxidative pyrolysis to share the same reaction pathways as autoxidation at lower temperatures, then the observed rate constants and activation energy may be calculated from kinetic parameters measured earlier for autoxidation of poly(propylene) from 71 to 140°C. Good agreement was obtained implying a similarity of oxidative degradation of the polymers spanning a large temperature range.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1980.021810105
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  • 7
    Electronic Resource
    Electronic Resource
    Investigation on the microstructure of poly(cyclohexyl α-chloroacrylate)s using 500 MHz 1H and 25 MHz 13C NMR (1986)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 375-381 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The tacticity of poly(cyclohexyl α-chloroacrylate) (PCCA) was studied by 500 MHz 1H and 25 MHz 13C NMR spectroscopy. The influence of the polymer configuration was observed at three different carbon resonances: The backbone methylene carbon, the carbonyl carbon and the quaternary carbon. Tetrad tacticities of PCCA measured from the resonance of the backbone methylene carbon were in good agreement with tetrad values obtained by 1H NMR. The polymer obtained was syndiotactic rich and obeyed Bernoullian statistics in its tacticity distribution.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1986.021870217
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  • 8
    Electronic Resource
    Electronic Resource
    High mileage catalysts for olefin polymerization, 34Part 33: cf. 1. Methanolysis of titanium, vanadium and chromium olefin polymerization catalysts (1993)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 194 (1993), S. 1639-1643 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 14CH3O3H was used to quench ethylene polymerization by transition metal catalysts. 3H labeling occurred exclusively for Ti-containing catalysts, whereas more than 95% of the chains were labeled with 14CH3 for the Cr-containing catalysts. Both modes of labeling occurred with V-containing catalysts. The observed phenomena indicate a change of “coordinate-carbanionic” to “coordinate-carbocationic” character for the alkyls of Ti, V and Cr in this order.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1993.021940611
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  • 9
    Electronic Resource
    Electronic Resource
    Regio- and stereo-selective alternating copolymerization of carbon monoxide with propene (1993)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 194 (1993), S. 2579-2603 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Compounds of palladium with ten different chelated bisphosphine ligands were investigated for their catalysis of alternating copolymerization of propene with carbon monoxide. The bisphosphine structure and chelate ring size influence strongly the activity, regio- and stereo-selectivity of the catalysts. Molecular mechanics calculations on the π-olefin complex showed that the non-bonded interaction between propene and the ligands on Pd is both regio- and stereo-selective. Primary insertion is about seven times more probable than secondary insertion for the Pd complex of bis(diphenylphosphino)butane ligand. The enantioselective catalysts favor the meso enchainment of propene. Gas chromatography/mass spectrometry (GC-MS) of oligomers showed that most chains are initiated by Pd—H species with less frequent initiation by Pd—OCH3 complexes; β-hydrogen elimination is the dominant chain termination process.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1993.021940915
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  • 10
    Electronic Resource
    Electronic Resource
    Properties of polyacetylene obtained with (η-Cp)2Ti(PMe3)2 (1989)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 1309-1317 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Acetylene was polymerized by (η-Cp)2Ti(PMe3)2 at room temperature to give predominantly trans-polyacetylene. All properties are within the ranges reported for polyacetylene produced with Ti(OBu)4/AlEt3 as catalyst.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1989.021900611
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