Syndiotactic polypropylene polymers

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Gorras, G., Tortora, M., Vittoria, V., Kaempfer, D., and Mulhaupt, R. 2003. Transport properties of organic vapors in nanocomposites of organophilic layered silicate and syndiotactic polypropylene. Polymer 44 3679-3685. 

Due to the presence of a high number of site epimerization errors, the microstructure of the syndiotactic polypropylene polymtas prepared with the catalyst system lO/MAO looks deceptively similar to the microstructure of the syndiotactic polypropylene polymers prepared via chain-end control mechanisms cf. [29] on syndiotactic polypropylene from [Me2Si(3,6- Bu2-9-lluoienyl) (N- Bu]TiCl2-based catalysts. 

Guadagno, L., Naddeo, C., Raimondo, M., Gorrasi, G., Vittoria, V. Effect of carbon nanotubes on the photo-oxidative durability of syndiotactic polypropylene. Polym. Degrad. Stab. 95, 1614-1626 (2010)... 

Polymers of different tacticity have quite different properties, especially in the solid state. One of the requirements for polymer crystallinity is a high degree of microstructural regularity to enable the chains to pack in an orderly manner. Thus atactic polypropylene is a soft, tacky substance, whereas both isotactic and syndiotactic polypropylenes are highly crystalline. 

Syndiotactic polypropylene has an ultimate melting point of 174°C, and extrapolated heat of fusion of 105 J/g (25.1 cal/g) both lower than those of isotactic polymer. The heat of fusion of the polymer produced using a metallocene catalyst is reported as 79 J/g (19 cal/g) (41). 

Syndiotactic polypropylene first became available in the 1990s (Fina, Mitsui Toastu, Sumitomo) and more recently has been marketed by Dow. Currently this polymer is more expensive than other polypropylenes both because of catalyst costs and the small scale of production. 

The propagating polymer then terminates, producing an isotactic polypropylene. Linear polyethylene occurs whether the reaction takes place by insertion through this sequence or, as explained earlier, by ligand occupation of any available vacant site. This course, however, results in a syndiotactic polypropylene when propylene is the ligand. 

The term tactidty refers to the configuration of polymer chains when their constituent monomer residues contain a steric center. Figure 1.8 illustrates the three principal classes of tacticity as exemplified by polypropylene. In isotactic polypropylene, the methyl groups are all positioned on the same side of the chain, as shown in Fig. 1.8 a). In syndiotactic polypropylene, the methyl groups alternate from one side to the other, as shown in Fig. 1.8 b). Random placement of the methyl groups results in atactic polypropylene, which is shown in Fig. 1.8 c). We can readily observe the effects of tacticity on the properties of polypropylene isotactic polypropylene is hard and stiff at room temperature, syndiotactic polypropylene is soft and flexible, and atactic polypropylene is soft and rubbery. 

Syndiotactic polypropylene became commercially available about ten years ago with the advent of single-site catalysts. Unlike its atactic and isotactic counterparts, its manufacture presented serious challenges to polymer scientists and engineers. Even under the best conditions, its syndiotacticity rarely exceeds 75%, based on pentad sequences. It typically has both a lower melting point (approximately 138 °C relative to approximately 155 to 160 °C) and density (0.89 g/cm3 relative to 0.93 g/cm3) than isotactic polypropylene. Syndiotactic polypropylene crystallites have a much more complex structure than the isotactic form, which impedes its crystallization. Therefore, in general, the syndiotactic form of polypropylene crystallizes very slowly. 

We will then examine other flexible polymer crystallization instances which may be interpreted, at least qualitatively, in terms of the bundle model. We will concentrate on crystallization occurring through metastable mesophases which develop by quenching polymers like isotactic polypropylene, syndiotactic polypropylene etc. In principle also hexagonal crystallization of highly defective polymers, and order developing in some microphase-separated copolymer systems could be discussed in a similar perspective but these two areas will be treated in future work. A comparison between the bundle approach and pertinent results of selected molecular simulation approaches follows. 

We examine briefly some specific instances starting with syndiotactic polypropylene (sPP). Aside from the already discussed hexagonal mesophase which can be obtained both drawing fibers and under quiescent conditions, this polymer presents four crystalline forms phases I [73] and II [74-76] where chains adopt the (T2G2)n helical conformation, forms III [30] and... 

The Dow corporation has recently developed constrained geometry addition polymerization catalysts (CGCT), typically Me2Si(C5Me4)(NBut)MCl2 (M = Ti, Zr, Hf) (141) activated with MAO. The homo-polymerization of a-olefins by CGCT afford atactic or somewhat syndiotactic (polypropylene rr 69%) polymers. The metal center of the catalyst opens the coordination sphere and enables the co-polymerization of ethylene to take place, not only with common monomers such as propylene, butene, hexene, and octene, but also with sterically hindered a-olefins such as styrene and 4-vinylcyclohexene [202]. 

The possible occurrence of a back-skip of the chain for catalytic systems based on C2-symmetric metallocenes would not change the chirality of the transition state for the monomer insertion and hence would not influence the corresponding polymer stereostructure. On the contrary, for catalytic systems based on Cs-symmetric metallocenes, this phenomenon would invert the chirality of the transition state for the monomer insertion, and in fact it has been invoked to rationalize typical stereochemical defects (isolated m diads) in syndiotactic polypropylenes.9 376 60 This mechanism of formation of stereoerrors has been confirmed by their increase in polymerization runs conducted with reduced monomer concentrations.65 In fact, it is reasonable to expect an increase in the frequency of chain back-skip by reducing the monomer concentration and hence the frequency of monomer insertion. 

Recently, a similar analysis of the conformational energy has been performed also for various new syndiotactic polymers.27,47 The conformational energy maps of syndiotactic polypropylene (sPP),48 polystyrene (sPS),49 poly butene (sPB),25 and poly(4-methyl-l-pentene) (sP4MP)26 are reported in Figure 2.12. A line repetition group s(M/N)2 for the polymer chain, and, hence, a succession of the torsion angles. .. 0i, 0i, 02, 02,..., has been... 

Under analogous conditions the spectrum of syndiotactic polypropylene is clearly distinguishable from that of the isotactic polymer but it, also, suffers from the same limitations. In both polymers it is difficult to determine the degree of stereoregularity with any accuracy. 

For syndiotactic polypropylene the symmetric Bernoulli trial, expressed in m and r dyads, is quite adequate for the representation of experimental data, and agrees with the stereochemical control being exerted by the growing chain end (145, 409). In its turn, atactic polypropylene is considered as a mixture of the products of two superposed processes, of the type discussed for isotactic and syndiotactic polymers, and is described by a simplified two-state model (145). 

For example, it is possible to synthesize isotactic as well as syndiotactic polypropylene in high configurational purity and high yields. The same holds for syndiotactic polystyrene. Furthermore, metallocene catalysts open the possibility to absolutely new homopolymers and copolymers like, e.g., cycloolefin copolymers (COG) and even (co)polymers of polar monomers.The simplest metallocene catalyst consists of two components. The first one is a n-complex (the actual metallocene) that can be bridged via a group X and therefore can become chiral ... 

Polypropylene (PP) is a semicrystalline commodity thermoplastic produced by coordination addition polymerization of propylene monomer [197]. Most frequently, stereospecific Ziegler-Natta catalysts are used in industrial processes to produce highly stereospecific crystalline isotactic (iPP) and syndiotactic (sPP) polymer with a small portion of amorphous atactic PP as a side product. Polymerization of non-symmetrical propylene monomer yields three possible sequences however, the steric effect related to the methyl side group highly favors the head-to-tail sequence. The occurence of head-to-head and tail-to-tail sequences produces defects along the PP chain [198]. Presence of such defects affects the overall degree of crystallinity of PP. 

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