Polypropylene coordination polymerization

In Section 6.21 we listed three main methods for polymerizing alkenes cationic, free-radical, and coordination polymerization. In Section 7.15 we extended our knowledge of polymers to their stereochemical aspects by noting that although free-radical polymerization of propene gives atactic polypropylene, coordination polymerization produces a stereoregulai polymer with superior physical properties. Because the catalysts responsible for coordination polymerization ar e organometallic compounds, we aie now in a position to examine coordination polymerization in more detail, especially with respect to how the catalyst works. 

Before coordination polymerization was discovered by Ziegler and applied to propene by Natta, there was no polypropylene industry. Now, more than 10 ° pounds of it aie prepared each year in the United States. Ziegler and Natta shared the 1963 Nobel Prize in chemistry Ziegler for discovering novel catalytic systems for alkene polymerization and Natta for stereoregular- polymerization. 

Transition metal catalysis plays a key role in the polyolefin industry. The discovery by Ziegler and Natta of the coordination polymerization of ethylene, propylene, and other non-polar a-olefins using titanium-based catalysts, revolutionized the industry. These catalysts, along with titanium- and zirconium-based metallocene systems and aluminum cocatalysts, are still the workhorse in the manufacture of commodity polyolefin materials such as polyethylene and polypropylene [3-6],... 

The first example of Iiving polyolefin with a uniform chain length was found in the low-temperature polymerization of propylene with the soluble catalyst composed of V(acac)3 and Al(C1Hi)2Cl. The mechanism of the living coordination polymerization is discussed on the basis of the kinetic and stereochemical data. Subsequently, some applications of living polypropylene are introduced to prepare tailor-made polymers such as terminally functionalized polymers and block copolymers which exhibit new characteristic properties. Finally, new types of soluble Ziegler-Natta catalysts are briefly surveyed in connection with the synthesis of living polyolefins. 

As mentioned in section 4.1, the kinetics of the living polypropylene synthesis have been interpreted in terms of a coordination polymerization mechanism represented by Eq. (22). We discuss here the mechanism of chain propagation on the basis of the structure and stereochemistry of the synthesized polypropylenes. 

Various types of well-defined block copolymers containing polypropylene segments have been synthesized by Doi et al. on the basis of three methods (i) sequential coordination polymerization of propylene and ethylene 83-m>, (ii) transformation of living polypropylene ends to radical or cationic ones which initiate the polymerization of polar monomers 104, u2i, and (iii) coupling reaction between iodine-terminated monodisperse polypropylene and living polystyrene anion 84). In particular, the well-defined block copolymers consisting of polypropylene blocks and polar monomer unit blocks are expected to exhibit new characteristic properties owing to the effect of microphase separation. 

Well-defined diblock (P—R) and triblock (P R — P) copolymers consisting of the polypropylene block (P) and the ethylene-propylene random copolymer block (R) were prepared by adding ethylene monomer during the living coordination polymerization of propylene with the soluble V(acac)3/Al(C2H5)2Cl/anisole catalyst U1). 

Polypropylene owes its current market success to the development of coordination polymerization. Before 1957 it was not produced commercially because radical polymerization gives an atactic polymer that is amorphous and has poor mechanical properties. Using a coordination catalyst, however, enables the production of an isotactic polymer that is semicrystalline. This material is stiff and hard and has a high tensile strength. Among its many useful products are rope, molded objects, and furniture. 

Coordination polymerization—A polymerization in which propagation occurs when monomer and a growing polymer chain both coordinate to a transition metal catalyst and then react. The final polymer often consists of one particular tacticity, e.g., isotactic polypropylene. 

Polyolefins have a central position in the marketplace of synthetic polymers, in terms of annual production volume . In the 1960s, Natta and coworkers reported that syndio-enriched polypropylene could be prepared by polymerization of propylene at —78°C in the presence of a mixture of vanadium tetrachloride and Et2AlCl . The molecular weight increased steadily for 25 h, and the polydispersity index (1.4 < My /M < 1.9) was moderately low °. This was the first hint of a possible control on this type of coordinative polymerization. 

Propylene monomer, like ethylene, is obtained from petroleum sources. Free-radical polymerizations of propylene and other a-olefins are completely controlled by chain transferring. It is therefore polymerized by anionic coordination polymerization. At present, mainly isotactic polypropylene is being used in large commercial quantities. There is some utilization of atactic polypropylene as well. Syndiotactic polypropylene, on the other hand, still remains mainly a laboratory curiosity. 

---