Chinese Journal of Applied Chemistry ›› 2010, Vol. 27 ›› Issue (06): 626-631.DOI: 10.3724/SP.J.1095.2010.90592

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Ethylene/1-Hexene Copolymer with Broadened Molecular Mass Distribution Obtained by Catalysis of  TiCl4/XROH/MgCl2/Et3Al

KONG Yuan1, WANG Hong-Li1, YI Jian-Jun2, ZHANG Ming-Ge2, HUANG Qi-Gu1*, YANG Wan-Tai1   

  1. (1.State Key Laboratory of Chemical Resource Engineering,Key Laboratory of Carbon Fiber
    and Functional Polymers,Ministry of Education,Beijing University of Chemical Technology,Beijing 100029;
    2.Laboratory for Synthetic Resin Research Institution of Petrochemical Technology,
    China National Petroleum Corporation,Beijing)
  • Received:2009-09-03 Revised:2009-11-30 Published:2010-06-10 Online:2010-06-10

Abstract:

The synthesis of copolymer with high comonomer incorporation and broadened molecular mass distribution from ethylene with 1-hexene catalyzed by co-catalyst TiCl4/XROH/MgCl2 and Et3Al is described. The influences of the catalyst system composition and the polymerization conditions on the behavior of ethylene/1-hexene copolymerization, the structure, molecular mass and molecular mass distribution(MMD) of the obtained copolymer have been discussed in detail. When the copolymerization was performed under the optimum conditions:n(Ti)∶n(Mg)=10∶1, n(XROH)∶n(MgCl2)=2.6∶1, n(Al)∶n(Ti)=100∶1, P=0.45 MPa, t=80 ℃, Time=2 h and the comonomer concentration in feed=0.25 mol/L, the catalytic activity reached 23.2 kg/g cat. The catalyst particle shape and the structure and properties of the ethylene/1-octene copolymer are characterized with 13C NMR, X-ray, SEM, WAXD, DSC and GPC. These results show that the catalytic activity, molecular mass distribution and higher 1-hexene incorporation were considerably improved when the multi-halogen alcohol(XROH) was added into the catalyst system. By adding XROH in the catalyst system made Ti mass fraction of the catalyst increased up to 4.8%; the molar ratio of MMD of the copolymer became broader, ranging from 15 to 20; 1-hexene incorporation within the copolymer chain was higher, up to 5.1%.

Key words: supported Z-N catalyst, multi-group internal donor, copolymer of olefins, broaden molecular weight distribution

CLC Number: