Characteristics of diether- and phthalate-based Ziegler-Natta catalysts for copolymerization of propylene and ethylene and terpolymerization of propylene, ethylene, and 1-butene

Copolymerization of propylene and ethylene and terpolymerization of propylene, ethylene, and 1-butene were carried out to compare the characteristics of diether- and phthalate-based Ziegler-Natta catalysts in a reaction system of pilot scale. The ethylene incorporation with the diether-based catalyst was higher but the 1-butene incorporation was lower compared with those of the phthalate-based catalyst. In the case of copolymers from the diether-based catalyst, melting behavior, determined through differential scanning calorimetry (DSC), showed a distinct shoulder peak and lots of nuclei were formed during crystallization. The diether-based catalyst led to polymers having blockier ethylene sequences compared with those of the phthalate-based catalyst; the highly crystallizable fraction (HIS) containing blockier ethylene sequences was produced with the diether-based catalyst. These results seem to be the result of regio-irregular characteristics of the diether-based catalyst. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 851-859, 2013

[1]  Toshiaki Taniike,et al.  Coadsorption model for first-principle description of roles of donors in heterogeneous Ziegler–Natta propylene polymerization , 2012 .

[2]  Aihua He,et al.  Copolymerization of propylene with 1‐octene catalyzed by MgCl2/TiCl4/diether catalyst , 2011 .

[3]  Jin-Yong Dong,et al.  Magnesium chloride supported Ziegler‐Natta catalysts containing succinate internal electron donors for the polymerization of propylene , 2010 .

[4]  G. D. Bukatov,et al.  Supported Ziegler–Natta catalysts for propylene polymerization. Study of surface species formed at interaction of electron donors and TiCl4 with activated MgCl2 , 2009 .

[5]  P. C. Thüne,et al.  The role of electron donors on lateral surfaces of MgCl2-supported Ziegler-Natta catalysts : Observation by AFM and SEM , 2008 .

[6]  J. C. Chadwick,et al.  Kinetic and Active Centre Studies on the Polymerization of Propylene using MgCl2 Supported Ziegler – Natta Catalysts and 1,3 Diether Donors , 2007 .

[7]  L. Cavallo,et al.  Key Elements in the Structure and Function Relationship of the MgCl2/TiCl4/Lewis Base Ziegler−Natta Catalytic System , 2007 .

[8]  N. Yabunouchi,et al.  Design of novel malonates as internal donors for MgCl2-supported TiCl4 type polypropylene catalysts and their mechanistic aspects, Part 1 , 2007 .

[9]  J. C. Chadwick,et al.  Active center determinations on MgCl2‐supported fourth‐ and fifth‐generation Ziegler–Natta catalysts for propylene polymerization , 2006 .

[10]  Zhicheng Zhang,et al.  Effect of diether as internal donor on MgCl2‐supported Ziegler–Natta catalyst for propylene polymerization , 2006 .

[11]  A. Rajantie.  Mass of a quantum 't Hooft-Polyakov monopole , 2005, hep-lat/0512006.

[12]  G. Talarico,et al.  Propene/ethylene-[1-13C] copolymerization as a tool for investigating catalyst regioselectivity. MgCl2/internal donor/TiCl4-external donor/AlR3 systems , 2004 .

[13]  J. C. Chadwick.  Advances in propene polymerization using MgCl2‐supported catalysts. Fundamental aspects and the role of electron donors , 2001 .

[14]  João B. P. Soares,et al.  Mathematical modelling of the microstructure of polyolefins made by coordination polymerization: a review , 2001 .

[15]  J. C. Chadwick,et al.  Effects of Internal and External Donors on the Regio- and Stereoselectivity of Active Species in MgCl2-Supported Catalysts for Propene Polymerization , 2001 .

[16]  L. Barino,et al.  Modeling of isospecific Ti sites in MgCl2 supported heterogeneous Ziegler-Natta catalysts , 1998 .

[17]  J. C. Chadwick,et al.  Propene polymerization with MgCl2‐supported catalysts: effects of using a diether as external donor , 1997 .

[18]  M. C. Sacchi,et al.  Microstructure Distribution of Polypropylenes Obtained in the Presence of Traditional Phthalate/Silane and Novel Diether Donors: A Tool for Understanding the Role of Electron Donors in MgCl2-Supported Ziegler-Natta Catalysts , 1996 .

[19]  J. C. Chadwick,et al.  Aspects of hydrogen activation in propene polymerization using MgCl2/TiCl4/diether catalysts , 1996 .

[20]  M. C. Sacchi,et al.  Polymerization Stereochemistry with Ziegler−Natta Catalysts Containing Dialkylpropane Diethers: A Tool for Understanding Internal/External Donor Relationships , 1996 .