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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 831-840 
    ISSN: 0887-624X
    Keywords: molecular weight distribution ; polyethylene ; soluble metallocene/MAO catalysts ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A critical look at the possibility of controlling the molecular weight distribution (MWD) of polyolefins by combining metallocene/methylalumoxane (MAO) catalysts is offered. Catalysts investigated were bis(cyclopentadienyl)zirconium dichloride (Cp2ZrCl2), its titanium and hafnium analogues (Cp2TiCl2 and Cp2HfCl2), as well as rac-ethylenebis(indenyl)zirconium dichloride (Et(Ind)2ZrCl2). As observed by other researchers, the MWD of polyethylene can be manipulated by combining soluble catalysts, which on their own produce polymer with narrow MWD but with different average molecular weights. Combined in slurry polymerization reactors, the catalysts in consideration produce ethylene homopolymer just as they would independently. Unimodal or bimodal MWDs can be obtained. This effect can be mimicked by blending polymers produced by the individual catalysts. We demonstrate how a variability in catalyst activity translates into a variability in MWD when mixing soluble catalysts in polymerization. Such a variability in MWD must be considered when setting goals for MWD control. We introduce a more quantitative approach to controlling the MWD using this method. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 831-840, 1998
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of seven poly(ethylene-co-1-octene) samples made with a single-site-type catalyst were analyzed by crystallization analysis fractionation (CRYSTAF). The samples have similar average copolymer compositions but differ in their average molecular weights. CRYSTAF results confirm the theoretical predictions of Stockmayer's distribution: the breadth of the chemical composition distribution is inversely proportional to the number average molecular weight for polymers made with single-site-type catalysts. Stockmayer's distribution was used to assess the instrumental peak broadening of CRYSTAF. An extension of this treatment for polyolefins made with multiple-site-type catalysts is proposed.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1022-1344
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An analytical solution for the distribution of molecular weight, long chain branching and chemical composition of polyolefins produced under steady-state conditions with the mechanism of terminal branching is derived. The model predictions agree well with Monte-Carlo simulation results. This detailed description of the microstructure of polymer chain populations with different levels of long chain branching can be useful in establishing structure-property relations for these polymers.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Theory and Simulations 4 (1995), S. 305-324 
    ISSN: 1022-1344
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Stockmayer bivariate distribution is used to qualitatively and quantitatively interpret TREF (temperature rising elution fractionation) spectra of polyolefins made by multiple site type catalysts. TREF spectra simulated by the proposed method can adequately fit experimental TREF data presented in the literature and can be used to help understand the mechanism of TREF separation and the nature of multiple site types catalysts.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Rapid Communications 19 (1998), S. 197-199 
    ISSN: 1022-1336
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The shape of the molecular weight distribution (MWD) of polyethylene produced with a bimetallic supported metallocene catalyst was controlled with hydrogen in a semi-batch slurry reactor. Polymers produced at different hydrogen pressures have MWD's varying from unimodal to bimodal, with high or low molecular weight shoulders.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Theory and Simulations 5 (1996), S. 547-572 
    ISSN: 1022-1344
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyolefins containing long chain branches can be synthesized using certain metallocene catalysts such as Dow Chemical's constrained geometry catalyst. These polyolefins combine the excellent mechanical properties of polymers with narrow molecular weight distribution with the easy processability of polymers containing long chain branches. A mathematical model for the chain length distribution for these novel polyolefins was derived from basic principles and an analytical solution for the chain length distributions of the populations containing different number of long chain branches per polymer molecule was obtained. The analytical solution agrees with the direct solution of the population balances and with a Monte-Carlo simulation model. It is also shown that this solution applies for copolymers using pseudo-kinetic rate constants and Stockmayer's bivariate distribution.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 1022-1344
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A generic mathematical model for analyzing the effect of ideal and non-ideal reactor residence time distributions on the size distribution of polymer particles produced with heterogeneous Ziegler-Natta and supported metallocene catalysts was developed. It was shown that the residence time distribution in polymerization reactors can have a significant effect on the size distribution of polymer particles and this can lead to imperfect replication of the catalyst particle size distribution.
    Additional Material: 18 Ill.
    Type of Medium: Electronic Resource
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