Effect of Chain Microstructure

All microstructural features impacting chain crystallizability can potentially influence the Crystaf fractionation process. The main microstructural properties of interest are (1) number average molecular weight, (2) CC, and (3) comonomer type. Each of these factors will be discussed below. 

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CareUa, J. M., Graessley, W. W., Fetters, L. J. Effects of chain microstructure on the viscoelastic properties of linear polymer melts Polybutadienes and hydrogenated polybutadienes. Macromol (1984) 17, pp. 2775-4647... 

The effect of branching is to increase the number of chain ends and, therefore, free volume, which decreases Tg. Conversely, crosslinking ties together separate molecules, decreases the number of loose ends, and raises Tg. Copolymers show different effects on T, depending on the microstructure... 

Experiments were conducted with a dual catalyst chain shuttling system in a continuous solution polymerization reactor. A series of ethylene-octene copolymers of similar melt index were produced with a composition of ca. 30% (by weight) hard and 70% soft blocks. The level of DEZ was systematically varied to study the effects of CSA ratio on polymer microstructure. 

The branched polymers produced by the Ni(II) and Pd(II) a-diimine catalysts shown in Fig. 3 set them apart from the common early transition metal systems. The Pd catalysts, for example, are able to afford hyperbranched polymer from a feedstock of pure ethylene, a monomer which, on its own, offers no predisposition toward branch formation. Polymer branches result from metal migration along the chain due to the facile nature of late metals to perform [3-hydride elimination and reinsertion reactions. This process is similar to the early mechanism proposed by Fink briefly mentioned above [18], and is discussed in more detail below. The chain walking mechanism obviously has dramatic effects on the microstructure, or topology, of the polymer. Since P-hydride elimination is less favored in the Ni(II) catalysts compared to the Pd(II) catalysts, the former system affords polymer with a low to moderate density of short-chain branches, mostly methyl groups. 

Conformational energies are calculated for chain segments in poly(vlnyl bromide) (PVB) homopolymer and the copolymers of vinyl bromide (VBS and ethylene (E), PEVB. Semlempirical potential functions are used to account for the nonbonded van der Waals and electrostatic Interactions. RIS models are developed for PVB and PEVB from the calculated conformational energies. Dimensions and dipole moments are calculated for PVB and PEVB using their RIS models, where the effects of stereosequence and comonomer sequence are explicitly considered. It is concluded from the calculated dimensions and dipole moments that the dipole moments are most sensitive to the microstructure of PVB homopolymers and PEVB copolymers and may provide an experimental means for their structural characterization. 

Subsequently, several nonkinetic approaches (32) were directed toward determining the structure of the live chain ends (e.g., H-NMR and 13C-NMR). For example, Bywater and co-workers (58) studied the addition of r-butyllithium to 1,3-butadiene and obtained a complex PMR spectrum for the addition product. They examined the effect of catalyst concentration on the microstructure of the polybutadiene and found that at high catalyst levels, the vinyl content increased as shown in Table II. 

The work of DiMarzio and Rubin (DiMarzio, 1965 Rubin, 1965 DiMarzio and Rubin, 1971) began the development of a related but more powerful approach. Rather than calculating microstructural details from a presumed architecture, Rubin s matrix method concentrates on the effect of local interactions on the propagation of the chain, thereby deriving the statistical properties of the random walk and the structure of the entire chain. This formalism is the foundation for several subsequent models, so some details are reviewed here. The notation is transposed into a form consistent with the contemporary models discussed below. 

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