Polymerization of vinyl chloride in the presence of modified Ziegler–Natta catalysts comprising long chain organoaluminum compounds

Florjańczyk, Zbigniew; Kuran, Witold; Sitkowska, Jadwiga; Ziółkowski, Andrzej

doi:10.1002/pola.1987.080250130

Cited by 3 publications

References 15 publications

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Ziegler‐Natta Polymerization

2010

Comprehensive Organic Name Reactions and Reagents

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This reaction involves a Lewis acid of an early transition metal (e.g., Ti, Zr, V, etc.) to catalyze the polymerization of vinyl monomers in the presence of trialkylaluminum to form stereoregulated or tactic polymers, and is generally known as the Ziegler–Natta polymerization or Ziegler–Natta olefin polymerization. Over the past half century, the Ziegler–Natta polymerization has been extensively improved, and several generations of Ziegler–Natta catalysts have been developed. On the basis of such seminal work, a variety of homogeneous catalysts have been explored, which can be divided into three groups. Further important developments for the Ziegler–Natta polymerization include the application of silyl or amido‐containing metallocenes as the catalysts as well as using organosilanes as polymer chain transfer reagents. More importantly, late transition metal (Ni, Pd) mediated polymerizations have been reported to afford highly branched polyethylene. It has been found that the stereoregulation is probably due to the fixed chiral orientation of the terminal CC bond of the growing polymer chain attaching to the catalytic site. The study finds that the isotactic polymers are commercially important, owing to their various favourable properties. In addition, the correct choice of electron donor for the MgCl 2 ‐supported TiCl 4 can also enhance the isotactic index (II). It has been found that the metallocenes with a C 2‐symmetry give isotactic polymers and syndiotactic polymers as represented by the highly isotactic (ethylenebis(tetrahydroindenyl))ZrC1 2 /MAO and syndiotactic isopropyl(cyclopentadieny1‐1‐fluorenyl)‐ZrC1 2 /MAO catalytic systems. Besides the tacticity, the molecular weight and molecular weight distribution (MWD) of the polymers also affect the properties of the polymers. It should be pointed out that the Ziegler–Natta polymerization is also good for the production of copolymers arising from different comonomers. Nevertheless, the Ziegler–Natta polymerization has some limitations.

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Ziegler‐Natta Polymerization

2010

Comprehensive Organic Name Reactions and Reagents

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From metal‐catalyzed radical telomerization to metal‐catalyzed radical polymerization of vinyl chloride: Toward living radical polymerization of vinyl chloride

Asandei

Percéc

2001

J. Polym. Sci. A Polym. Chem.

122

116

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The metal-catalyzed radical polymerization of vinyl chloride (VC) in orthodichlorobenzene initiated with various activated halides, such as ␣,␣-dihaloalkanes, ␣,␣,␣-trihaloalkanes, perfloroalkyl halides, benzyl halides, pseudohalides, allyl halides, sulfonyl halides, ␣-haloesters, ␣-halonitriles, and imidyl halides, in the presence of Cu(0)/2,2Ј-bipyridine, Fe(0)/o-phenantroline, TiCp 2 Cl 2 , and other metal catalysts is reported. The formation of the monoadduct between the initiator and VC was achieved with all catalysts. However, propagation was observed only for metals in their zero oxidation state because they were able to reinitiate from geminal dihalo or allylic chloride structures. Poly(vinyl chloride) with molecular weights larger then the theoretical limit allowed by chain transfer to VC were obtained even at 130°C. In addition, the most elemental features of a living radical polymerization, such as a linear dependence of the molecular weight and a decrease of polydispersity with conversion, were observed for the most promising systems based on iodine-containing initiators and Cu(0), that is, IOCH 2 OPhOCH 2 OI/Cu(0)/bpy (where bpy ϭ 2,2Ј-bipyridyl), at 130°C. However, because of the formation of inactive species via chain transfer to VC and other side reactions, the observed conversions were in most cases lower than 40%. A mechanistic interpretation of the chain transfer to monomer in the presence of Cu species is proposed.

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Homopolymerization and copolymerization of vinyl chloride over supported metalorganic catalysts

Kovaleva

Новокшонова

2016

Kinet Catal

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Polymerization of vinyl chloride in the presence of modified Ziegler–Natta catalysts comprising long chain organoaluminum compounds

Cited by 3 publications

References 15 publications

Ziegler‐Natta Polymerization

Ziegler‐Natta Polymerization

From metal‐catalyzed radical telomerization to metal‐catalyzed radical polymerization of vinyl chloride: Toward living radical polymerization of vinyl chloride

Homopolymerization and copolymerization of vinyl chloride over supported metalorganic catalysts

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