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Terunori Fujita – One of the best experts on this subject based on the ideXlab platform.

Yasuhiko Suzuki – One of the best experts on this subject based on the ideXlab platform.

Ricardo Reich – One of the best experts on this subject based on the ideXlab platform.

Zhiqiang Fan – One of the best experts on this subject based on the ideXlab platform.

  • effects of comonomer on active center distribution of tcl4 mgcl2 alet3 catalyst in ethylene 1 Hexene copolymerization
    Journal of Organometallic Chemistry, 2015
    Co-Authors: Hongrui Yang, Zhiqiang Fan
    Abstract:

    Abstract Ethylene/1Hexene copolymerization with MgCl2/TiCl4–AlEt3 catalyst has been conducted under different initial 1Hexene concentration (0–0.5 mol/L). Number of polymerization active centers was determined by quenching the reaction with 2-thiophenecarbonyl chloride and measuring sulfur content of the quenched polymer. Each copolymer sample was fractionated into boiling n-heptane soluble and insoluble fractions, and active centers in these fractions were also counted. The rate constants of ethylene and 1Hexene insertion in the active centers were calculated, respectively. Molecular weight distribution (MWD) curves of the polymers were deconvoluted with 4–5 Flory components, and changes of activity of the Flory components with [1Hexene] were analyzed. The polymerization activity and the number of active centers were significantly enhanced by increasing [1Hexene]. Large number of active centers were revived by small amount of 1Hexene. With the increase of [1Hexene], the number of active centers producing polymer chains with lower molecular weight and higher 1Hexene content was increased more than those producing polymer chains with higher molecular weight and lower 1Hexene content, and the MWD curve continuously inclined to the low molemolecular weight side. The active centers with higher 1Hexene incorporation rate have relatively smaller rate constant of ethylene insertion. When [1Hexene] was increased, the rate constant of ethylene insertion was only slightly changed, but the rate constant of 1Hexene insertion was markedly lowered, meaning that the active centers revived by 1Hexene have relatively lower ability of incorporating 1Hexene.

  • Effects of comonomer on active center distribution of TCl4/MgCl2–AlEt3 catalyst in ethylene/1Hexene copolymerization
    Journal of Organometallic Chemistry, 2015
    Co-Authors: Hongrui Yang, Zhiqiang Fan
    Abstract:

    Abstract Ethylene/1Hexene copolymerization with MgCl2/TiCl4–AlEt3 catalyst has been conducted under different initial 1Hexene concentration (0–0.5 mol/L). Number of polymerization active centers was determined by quenching the reaction with 2-thiophenecarbonyl chloride and measuring sulfur content of the quenched polymer. Each copolymer sample was fractionated into boiling n-heptane soluble and insoluble fractions, and active centers in these fractions were also counted. The rate constants of ethylene and 1Hexene insertion in the active centers were calculated, respectively. Molecular weight distribution (MWD) curves of the polymers were deconvoluted with 4–5 Flory components, and changes of activity of the Flory components with [1Hexene] were analyzed. The polymerization activity and the number of active centers were significantly enhanced by increasing [1Hexene]. Large number of active centers were revived by small amount of 1Hexene. With the increase of [1Hexene], the number of active centers producing polymer chains with lower molecular weight and higher 1Hexene content was increased more than those producing polymer chains with higher molecular weight and lower 1Hexene content, and the MWD curve continuously inclined to the low molemolecular weight side. The active centers with higher 1Hexene incorporation rate have relatively smaller rate constant of ethylene insertion. When [1Hexene] was increased, the rate constant of ethylene insertion was only slightly changed, but the rate constant of 1Hexene insertion was markedly lowered, meaning that the active centers revived by 1Hexene have relatively lower ability of incorporating 1Hexene.

  • COPOLYMERIZATION OF ETHYLENE AND 1Hexene WITH TiCl4/MgCl2 CATALYSTS MODIFIED BY 2,6-DIISOPROPYLPHENOL *
    Chinese Journal of Polymer Science, 2012
    Co-Authors: Shengjie Xia, Xiao-yan Liu, Zhiqiang Fan
    Abstract:

    A supported TiCl4/MgCl2 catalyst without internal electron donor (O-cat) was prepared firstly. Then it was modified by 2,6-diisopropylphenol to make a novel modified catalyst (M-cat). These two catalysts were used to catalyze ethylene/1Hexene copolymerization and 1Hexene homopolymerization. The influence of cocatalyst and hydrogen on the catalytic behavior of these two catalysts was investigated. In ethylene/1Hexene copolymerization, the introduction of 2,6- i Pr2C6H3O- groups did not deactivate the supported TiCl4/MgCl2 catalyst. Although the 1Hexene incorporation in ethylene/1Hexene copolymer prepared by M-cat was lower than that prepared by O-cat, the composition distribution of the former was narrower than that of the latter. Methylaluminoxane (MAO) was a more effective activator for M-cat than triisobutylaluminium (TIBA). MAO led to higher yield and more uniform chain structure. In 1Hexene homopolymerization, the presence of 2,6- i Pr2C6H3O- groups lowered the propagation rate constants. Two types of active centers with a chemically bonded 2,6- i Pr2C6H3O- group were proposed to explain the observed phenomena in M-cat.

Sonia Loras – One of the best experts on this subject based on the ideXlab platform.