Isotactic-atactic stereoblock polypropylene

Waymouth and coworkers reported a unique system where the unbridged bis(2-phenylindenyl)zirconium-based catalysts (129) gave elastomeric, isotactic-atactic stereoblock polypropylene, controlled by rotation of the 2-phenylindenyl as shown in Scheme VII [173]. 

Natta also serendipitously isolated polypropylene fractions that exhibited novel elastomeric behavior that he proposed were a manifestation of properties linked to an unique isotactic-atactic stereoblock polypropylene (sbPP) microstructure (Vll in Figure 3.1) [13]. In this model, the elastic properties of sbPP were hypothesized to originate with interchain associations of hard, crystalline isotactic) domains that function as nonbonded physical crosslinks within an amorphous atactic) matrix, with the former serving to dimensionally restore the material upon the removal of a deforming strain. Unfortunately, this sbPP material was not the principal product of a controlled polymerization for which a sound mechanism could be established to account for chain growth that, in this case, must proceed in alternating stereoselective and nonselective fashion. Indeed, both sPP and sbPP... 

Figure 22.11. Unsymmetrical catalysts that form isotactic-atactic stereoblock polypropylene.

For a recent example of stereoblock-isotactic polypropylenes assumed to be isotactic/atactic stereoblock polypropylenes, see De Rosa, C. Auriemma, F. Circelli, T. Waymouth, R. M. Crystallization of the a and y forms of isotactic polypropylene as a tool to test the degree of segregation of defects in the polymer chains. Macromolecules 2002, 55, 3622-3629. 

MAJOR APPLICATIONS The polymers referred to in this chapter include those families of homopolymers of propylene which are known to have elastomeric recovery properties at reasonable molecular weight and for which properties have been attributed to a crystallizable-noncrystallizable (e.g., isotactic-atactic) stereoblock structure, or to a major component with a stereoblock structure, whether or not the compositions are homogeneous by solvent fractionation tests. Copol)rmers and blends are not deliberately included in the data presented, but are described in some of the references. (See also some of the closely related elastomeric polymers presented in the entry on Polypropylene, atactic in this handbook.) The criterion of multiple crystallizable blocks per polymer chain may be met in significant fractions of low-tacticity, low-stereoregularity polymers of very high molecular weight. 

Pathway (1) has recently found an interesting demonstration in the related area of ethylene/1-alkene multiblock copolymerization, with ZnR2 acting as the chain shuttling agent. In propylene homopolymerization, presumptive evidence of isotactic/atactic stereoblock chain formation with a similar mechanism was reported by Chien et al. for polypropylenes obtained with mixtures of... 

During the last decade, a variety of new catalysts have been presented for the stereospecific polymerisation of a-olefins, based on non-bridged metallocene or stereorigid ansa-metallocene as the procatalyst and a methylaluminoxane activator [29,30,37,105-107,112-114,116-135], Apart from isotactic [118,119,124, 131,132] and syndiotactic [23,118,124,133] polypropylenes and other poly(a-olefin)s [121], hemiisotactic [112,121,124], isoblock [131,132,134], syndioiso-block (stereocopolymer) [127], stereoblock isotactic [135] and stereoblock isotactic atactic [116,128,129] polypropylenes have been obtained using these new catalysts. 

Propylene polymerisation with class I and class II catalysts gives rise, in principle, to atactic polypropylene, with class III catalysts to isotactic polypropylene [22] and with class IV catalysts to syndiotactic polypropylene [23], while for the less symmetric class V catalysts no general prediction is possible. In specific cases, however, isotactic, hemiisotactic, stereoblock isotactic attactic as well as syndiotactic polypropylenes can be obtained with class V catalysts, depending on their kind [107,112,116,124,127,137]. 

Polypropylenes with low amounts of ohgomers atactic, isotactic, isoblock, stereoblock, and syndiotactic... 

Stereoblock polypropylene is synthesized by unbridged metallocenes such as bis(neomenthyl)zirconium dichloride (7) with cyclopentadienyl or phenyl substituted indenyl ligands [55, 56]. The stereoblock length increases at lower polymerization temperatures. Products containing isotactic and atactic blocks are elastomeric if the isotactic block length is short. Rieger [57] obtained similar polypropylenes by bridged fluorenyl-substituted indenyl zirconium complexes. 

In addition to polypropylenes in which the entire polymer chain consists of isotactic, syndiotactic, hemiisotactic, or atactic chains, polypropylenes in which the chain consists of alternating blocks of two microstructures have been prepared. Perhaps the most interesting and useful of these stereoblock polymers consists of the combination of a crystalline block, such as a unit of isotactic or syndiotactic polypropylene, and an amorphous block, such as atactic polypropylene. Polymers containing this combination of microstructures often behave as a thermoplastic elastomer and have properties... 

The most recent expansion of the metallocene catalyst families is represented by oscillating metallocenes such as bis(2-phenyl-indenyl)2ZrCl2, developed by Coates and Waymouth [28]. Rotation of the phenyl-substituted indenyl ligand accounts for formation of isoselective racemic and non-stereoselective meso-stereoisomers of the metallocene. Provided the isomerization rate is rapid in comparison to the chain propagation rate, segmented polypropylene is obtained, where crystalline isotactic and amorphous atactic segments alternate. The formation of such stereoblock polypropylenes is displayed in Fig. 13a and 13b. The ratio of amorphous and crystalline segments is controlled by polymerization temperature and monomer... 

Figure 21 Proposed mechanism for stereoblock isotactic/atactic polypropylene formation.

As stated above, we postulated that fast, reversible chain transfer between two different catalysts would be an excellent way to make block copolymers catalytically. While CCTP is well established, the use of main-group metals to exchange polymer chains between two different catalysts has much less precedent. Chien and coworkers reported propylene polymerizations with a dual catalyst system comprising either of two isospecific metallocenes 5 and 6 with an aspecific metallocene 7 [20], They reported that the combinations gave polypropylene (PP) alloys composed of isotactic polypropylene (iPP), atactic polypropylene (aPP), and a small fraction (7-10%) claimed by 13C NMR to have a stereoblock structure. Chien later reported a product made from mixtures of isospecific and syndiospecific polypropylene precatalysts 5 and 8 [21] (detailed analysis using WAXS, NMR, SEC/FT-IR, and AFM were said to be done and details to be published in Makromolecular Chemistry... 

The atactic amorphous portion (9-16% of the total) contained in the obtained polypropylene has been separated by treating the raw polymer with n-heptane at room temperature. When operating in such a way, we have not separated the stereoblock fraction (extractable in boiling n-hep-tane) from the isotactic (not extractable in boiling n-heptane) fraction of polymer. The results reported in this paper are generally referred to the crystalline fraction, named non-atactic, which contains also some stereoblock polymers (at the considered polymerization temperatures, the latter generally correspond only to 5-7 % of the total) (9)... 

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