STEREOCHEMISTRY OF POLYMERIZATION in .NET

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STEREOCHEMISTRY OF POLYMERIZATION
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8-3b 8-3b-1
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Ionic and Coordination Polymerizations Effect of Coordination
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For ionic chain polymerizations in solvents with high solvating power where solvent-separated ion-pair- or free-ion-propagating species are involved, the factors governing the stereochemistry of the reaction are similar to those for radical polymerization. Syndiotactic polymerization is increasingly favored as the polymerization temperature is lowered. When polymerizations are carried out in solvents with poor solvating power, there is extensive coordination among the initiator, propagating chain end, and monomer, and the stereochemical result can be quite different. In the usual case, propagation is prevented from taking place by one or the other of the two placements (R- or S-) as coordination becomes the dominant driving force for stereoselectivity in the polymerization. The kr =km ratio tends toward a value of zero, and isoselective polymerization occurs. Coordination can yield syndioselective polymerization in some systems. Table 8-2 shows some examples of the early stereoselective polymerizations. The MMA and isobutyl vinyl ether polymerizations involve initiators and reaction conditions discussed previously (Chap. 5) without consideration of stereochemistry. The rst reported instance of stereoselective polymerization was probably the cationic polymerization of isobutyl vinyl ether in 1947 [Schildknecht et al., 1947]. A semicrystalline polymer was obtained when the reaction was carried out at 80 to 60 C using boron tri uoride etherate as the initiator with propane as the solvent. The full signi cance of the polymerization was not realized at the time as the crystallinity was attributed to a syndiotactic structure. X-Ray diffraction in 1956 indicated that the polymer was isotactic [Natta et al., 1956a,b]. (NMR would have easily detected the isotactic structure, but NMR was not a routine tool in 1947.) Stereoselective polymerization came into existence in the mid-1950s with the work of Ziegler in Germany and Natta in Italy. Ziegler was studying the reactions of ethylene catalyzed with trialkylaluminum at high temperatures and pressures. Both oligomerization to higher 1-alkenes and polymerization occurred. The highest polymer molecular weights achieved were 5000. The addition of a transition metal compound to trialkylaluminum had a dramatic effect on the polymerization. High-molecular-weight polyethylene (PE) was formed at low temperatures (50 100 C) and low pressures [Ziegler, 1964; Ziegler et al., 1955]. This PE is much less branched and has property enhancements compared to PE
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TABLE 8-2 Stereoselective Polymerizations Monomer Isobutyl vinyl ether
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Reaction Conditions BF3 etherate in propane at 80 to 60 C fMgBr (30 C) or n-C4 H9 Li ( 78 to 0 C) in fCH3 n-C4 H9 Li in THF at 78 C TiCl4 , (C2 H5 )3 Al in n-heptane at 50 C VCl4 , (C2 H5 )3 Al, fOCH3 in fCH3 at 78 C
Polymer Structure Isotactic Isotactic Syndiotactic Isotactic Syndiotactic
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Methyl methacrylateb Methyl methacrylateb Propenec Propened
Data from Schildknecht et al. [1947]. Data from Yuki et al. [1975]. c Data from Natta et al. [1958]. d Data from Zambelli et al. [1963].
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FORCES OF STEREOREGULATION IN ALKENE POLYMERIZATIONS
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produced by radical polymerization; see Sec. 8-11). Natta used Ziegler s initiators to achieve stereoselective polymerizations (both isoselective and syndioselective) of propene and other 1-alkenes (a-ole ns) [Natta, 1965]. This was a huge achievement since a-ole ns cannot be polymerized to high-molecular-weight polymer by radical or other ionic initiators (Secs. 3-7c, 5-2b). The scienti c and practical signi cance of their work earned Natta and Ziegler the joint award of the 1963 Nobel Prize in Chemistry [Mulhaupt, 2003]. The work of Ziegler and Natta led to the development of a very large number of twocomponent initiator systems consisting of an organometallic compound or hydride of a group I III metal together with a halide or other derivative of a group IV VIII transition metal [Pasquon et al., 1989]. The polymerizations are generally carried out in a hydrocarbon solvent such as n-hexane. The more important component of the initiator system is the transition metal compound. The function of the group I III metal compound is to modify and activate the transition metal compound for initiation. Some of the compounds used as the group I III metal component are triethylaluminum, diethylaluminum chloride, and diethylzinc; titanium trichloride or tetrachloride, vanadium trichloride, and chromium triacetylacetonate are examples of the transition metal component [Choi and Ray, 1985; Corradini et al., 1989; Pino et al., 1987; Tait, 1989]. These initiator systems are the traditional Ziegler Natta initiators. The actual initiator species have not been isolated, and their structures are not well understood. One mixes the two components, perhaps adds some other compounds for enchancements in reactivity and/or stereoselectivity, and then adds the mixture (which usually is heterogeneous) to the monomer the result is enormously useful stereoselective polymerizations. These were still the initiators used in more than 95% of commercial processes in 2002. Since the mid-1980s there has been another revolution the discovery and development of metallocene initiators within the Ziegler Natta revolution. Bis(cyclopentadienyl)titanium dichloride and bis(indenyl)zirconium dichloride are examples of simple metallocene initiators. More complex metallocenes have substituents on the organic ligands and the ligands are joined together through 2 CH2 and other bridges. The metallocene initia CH tors, unlike the traditional Ziegler Natta initiators, are molecules that can be isolated, analyzed by techniques such as NMR, and puri ed. Metallocene initiators are also homogeneous in the reaction systems. They offer the potential for tailor-making initiators to perform highly stereoselective polymerizations of speci c monomers. Utilization of the metallocene initiators requires the addition of a group I III metal compound, as in the case of the traditional Ziegler Natta initiators. Some clari cation is needed regarding terminology. The metallocene initiators are a type of Ziegler Natta initiator, derived from a combination of a transition and group I III metal compounds. However, the growing importance of metallocenes leads us to distinguish them from the traditional Ziegler Natta initiators by using the term metallocene. All of these initiators can be considered as coordination initiators, initiators that perform stereoselectively due to coordination. This term includes initiators other than the Ziegler Natta and metallocene initiators; examples are n-butyllithium, phenylmagnesium bromide, and boron tri uoride. Polymerizations brought about by coordination initiators are referred to as coordination polymerizations. The terms isoselective and syndioselective are used to describe initiators and polymerizations that produce isotactic and syndiotactic polymers, respectively. 8-3b-2 Mechanism of Stereoselective Placement
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Coordination initiators perform two functions. First, they supply the species that initiates the polymerization. Second, the fragment of the initiator aside from the initiating portion has unique coordinating powers. Coordination of this fragment (which may be considered as
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