In situ copolymerization of ethylene to produce linear low‐density polyethylene by Ti(OBu)4/AlEt3‐MAO/SiO2/Et(Ind)2ZrCl2

Linear low-density polyethylene (LLDPE) is produced in a reactor from single ethylene feed by combining Ti(OBu)4/AlEt3, capable of forming α-olefins (predominantly 1-butene), with SiO2-supported Et(Ind)2ZrCl2 (denoted MAO/SiO2/Et(Ind)2ZrCl2), which is able to copolymerize ethylene and 1-butene in situ with little interference in the dual-functional catalytic system. The two catalysts in the dual-functional catalytic system match well because of the employment of triethylaluminum (AlEt3) as the single cocatalyst to both Ti(OBu)4 and MAO/SiO2/Et(Ind)2ZrCl2, exhibiting high polymerization activity and improved properties of the obtained polyethylene. There is a noticeable increment in catalytic activity when the amount of Ti(OBu)4 in the reactor increases and 1-butene can be incorporated by about 6.51 mol % in the backbone of polyethylene chains at the highest Ti(OBu)4 concentration in the feed. The molecular weights (Mw), melting points, and crystallinity of the LLDPE descend as the amount of Ti(OBu)4 decreases, which is attributed mainly to chain termination and high branching degree, while the molecular weight distribution remains within a narrow range as in the case of metallocene catalysts. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2451–2455, 2004

[1]  G. Bazan,et al.  Triple tandem catalyst mixtures for the synthesis of polyethylenes with varying structures. , 2002, Journal of the American Chemical Society.

[2]  G. Bazan,et al.  Synthesis of Branched Polyethylene by Tandem Catalysis , 2001 .

[3]  G. Bazan,et al.  Synthesis of Branched Polyethylene from Ethylene by Tandem Action of Iron and Zirconium Single Site Catalysts , 2001 .

[4]  T. Marks,et al.  Cocatalysts for metal-catalyzed olefin polymerization: activators, activation processes, and structure-activity relationships. , 2000, Chemical reviews.

[5]  G. Bazan,et al.  Synthesis of Butene−Ethylene and Hexene−Butene−Ethylene Copolymers from Ethylene via Tandem Action of Well-Defined Homogeneous Catalysts , 2000 .

[6]  R. Benavente,et al.  Synthesis and characterization of copolymers of ethylene and 1-octadecene using the rac-Et(Ind)2ZrCl2/MAO catalyst system , 1999 .

[7]  G. Bazan,et al.  Synthesis of Branched Polyolefins Using a Combination of Homogeneous Metallocene Mimics , 1998 .

[8]  René S. Rojas,et al.  Study of the effect of the monomer pressure on the copolymerization of ethylene with 1-hexene , 1997 .

[9]  R. S. Mauler,et al.  Determination of reactivity ratios for ethylene/α-olefin copolymerization catalysed by the C2H4[Ind]2ZrCl2/methylaluminoxane system , 1996 .

[10]  W. Bras,et al.  Dynamic DSC, SAXS and WAXS on homogeneous ethylene-propylene and ethylene-octene copolymers with high comonomer contents , 1996 .

[11]  J. Koivumäki Properties of ethylene/1-octene, 1-tetradecene and 1-octadecene copolymers obtained with Cp2ZrCl2/MAO catalyst: effect of composition and comonomer chain length , 1996 .

[12]  J. Dupont,et al.  Copolymerization of ethylene with 1‐hexene and 1‐octene: correlation between type of catalyst and comonomer incorporated , 1995 .

[13]  L. Resconi,et al.  1-olefin polymerization at bis(pentamethylcyclopentadienyl)zirconium and -hafnium centers : enantioface selectivity , 1992 .

[14]  J. Chien,et al.  Syndiospecific polymerization of styrene. 3. Catalyst structure , 1992 .

[15]  W. Kaminsky,et al.  Comparison of zirconocene and hafnocene catalysts for the polymerization of ethylene and 1-butene† , 1992 .

[16]  J. Chien,et al.  Olefin copolymerization with metallocene catalysts. I. Comparison of catalysts , 1991 .

[17]  J. Chien,et al.  Olefin copolymerization with metallocene catalysts. III. Supported metallocene/methylaluminoxane catalyst for olefin copolymerization , 1991 .

[18]  G. Fink,et al.  Part II: A New Type of α Olefin Polyyxrization With Ni(O)/Phosphorane Catalysts , 1986 .

[19]  L. P. Lindeman,et al.  Carbon-13 nuclear magnetic resonance spectrometry. Chemical shifts for the paraffins through C9 , 1971 .