Ziegler Natta stereoregularity

When the insertion of propylene molecules in the growing chain is such that all methyl branches are on the same hand, the regularity of the chain allows it to crystallize this is the isotactic polypropylene (iPP), synthesized by Natta [8, 9] and the most commercial type obtained by the Ziegler-Natta stereoregular polymerization process. When the monomer insertion is consistently in the opposite hand to previous monomer insertion, the polymer obtained is syndiotactic polypropylene (sPP), which achieves lower crystallinity and today has less commercial interest. The random stereo incorporation of monomer units results in an amorphous resin, atactic polypropylene (aPP). 

Ziegler-Natta stereoregular polymerisation of a-olefins and dienes was discovered in 1954. This reaction opened opportunities for the synthesis of various stereoregular olefins and dienes. It occurs in the presence of catalytic systems, formed by organic... 

Among other possible reactions, these free radicals can initiate ordinary free-radical polymerization. The Ziegler-Natta systems are thus seen to encompass several mechanisms for the initiation of polymerization. Neither ionic nor free-radical mechanisms account for stereoregularity, however, so we must look further for the mechanism whereby the Ziegler-Natta systems produce this interesting effect. 

The primary use of TiCl is as a catalyst for the polymerisa tion of hydrocarbons (125—129). In particular, the Ziegler-Natta catalysts used to produce stereoregular polymers of several olefins and dienes, eg, polypropylene, are based on a-TiCl and A1(C2H3)3. The mechanism of this reaction has been described (130). SuppHers of titanium trichloride iaclude Akso America and Phillips Petroleum ia the United States, and Mitsubishi ia Japan. 

Even more important is the stereoregular catalytic polymerization of ethene and other alkenes to give high-density polyethene ( polythene ) and other plastics. A typical Ziegler-Natta catalyst can be made by mixing TiCU and Al2Eti in heptane partial reduction to Ti " and alkyl transfer occur, and a brown suspension forms which rapidly absorbs and polymerizes ethene even at room temperature and atmospheric pressure. Typical industrial conditions are 50- 150°C and 10 atm. Polyethene... 

Ziegler-Natta catalysts currently produce linear polyethylene (non-branched), stereoregular polypropylene, cis-polybutadiene, and other stereoregular polymers. 

Alkene polymerization can be carried out in a controlled manner using a Ziegler-Natta catalyst. Ziegler-Natta polymerization minimizes the amount of chain branching in the polymer and leads to stereoregular chains—either isotactic (substituents on the same side of the chain) or syndiotactic (substituents on alternate sides of the chain), rather than atactic (substituents randomly disposed). 

Alkenes undergo addition polymerization. When a Ziegler-Natta catalyst is used, the polymer is stereoregular and has a high density. 

We can employ coordination polymerization to produce stereoregular polystyrene. By performing this type of reaction at low temperatures, using Ziegler-Natta or single-site catalysts, we can prepare isotactic and syndiotactic versions of polystyrene. 

Ziegler-Natta catalysts are used commercially for the production of stereoregular polymers, especially isotactic polypropylene and high-density linear polyethylene. The resultant polymers have number and weight average molecular weights (Mn and Mw, respectively) that are defined as... 

Natta A process for polymerizing propylene and other higher olefins, catalyzed by crystalline titanium trichloride and an alkyl aluminum compound such as triethyl aluminum. The polymer can exhibit various types of stereoregularity, depending on the catalyst and the conditions. Invented in 1954 by G. Natta at the Istituto de Chimica Industrial del Politecnico di Milano, Italy, and commercialized in 1957. Now used widely, worldwide. See also Ziegler, Ziegler-Natta. 

Chapter 1, by Guerra, Cavallo, and Corradini, discusses in detail both the historical and modem aspects of stereoregular olefin polymerization, a field that arose with the first uses of the catalyst that came to be known as Ziegler-Natta, and a field that these authors greatly contributed to and therefore write about with an intimate knowledge. 

Ziegler-Natta catalyst. Gi ulio Natta developed a catalyst based on his work with Karl Ziegler for polymerizing vinyl monomers to give stereoregular, tailored, three-dimensional chains. The catalyst is based on aluminum alkyls and TiCU or other transition metal halides. 

Ziegler-Natta (or Natta-Ziegler) catalyst (ZNC) Able to produce stereoregular pol5uners. zwitterionic polymerization Copolymerization between nucleophilic and electrophilic comonomers. 

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