Syndiotactic polymers conformation

Conformational Energy Calculations in Isotactic and Syndiotactic Polymers... 

Interesting geometrical differences between helical conformations in isotactic and syndiotactic polymers have recently been found.25 27... 

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... 

Figure 2.12 Maps of conformational energy of various syndiotactic polymers as function of backbone torsion angles 0 and 0227 (a) syndiotactic polystyrene, (b) polypropylene, (c) poly (1-butene), and (d) poly(4-methyl-l-pentene). Succession of torsion angles. .. 0i 0i 0202 - - -[s(M/N)2 symmetry] has been assumed. Isoenergetic curves are reported every 5 kJ/mol of monomeric units with respect to absolute minimum of each map assumed as zero. Values of energies corresponding to minima (x) are also indicated. Experimental conformations observed for different polymorphic forms of polymers are indicated by triangles. (Reproduced with permission from Ref. 27. Copyright 1992 by the Socicta Chimica Italiana.)...

Models of the chain conformations found in the various polymorphic forms of syndiotactic polymers are reported in Figure 2.13. 

When A A or B B, the symmetry is lower and the only possible line repetition groups are s(M/N) and tc for isotactic and syndiotactic polymers, respectively, in both cis and trans configurations. In these cases, two independent torsion angles in the main chain define the regular conformation (Oi and 02 in Figure 2.15). 

Mesomorphic forms characterized by conformationally ordered polymer chains packed in lattices with different kinds of lateral disorder have been described for various isotactic and syndiotactic polymers. For instance, for iPP,706 sPP,201 sPS,202 syndiotactic poly(p-methylstyrene) (sPPMS),203 and syndiotactic poly(m -methylstyrene),204 mesomorphic forms have been found. In all of these cases the X-ray fiber diffraction patterns show diffraction confined in well-defined layer lines, indicating order in the conformation of the chains, but broad reflections and diffuse haloes on the equator and on the other layer lines, indicating the presence of disorder in the arrangement of the chain axes as well as the absence of long-range lateral correlations between the chains. 

The butadiene polymers represent another cornerstone of macromolecular stereochemistry. Butadiene gives rise to four different types of stereoregular polymers two with 1,2 linkage and two with 1,4. The first two, isotactic (62) and syndiotactic (25), conform to the definitions given for vinyl polymers, while the latter have, for eveiy monomer unit, a disubstituted double bond that can exist in the two different, cis and trans, configurations (these terms are defined with reference to the polymer chain). If the monomer units all have the same cis or trans configuration the polymers are called cis- or trans-tactic (30 and 31). The first examples of these stereoisomers were cited in the patent literature as early as 1955-1956 (63). Structural and mechanistic studies in the field have been made by Natta, Porri, Corradini, and associates (65-68). 

Because atactic polymer has no ordered structure and shows only slight intramolecular interactions, the interactions between atactic polymers is the strongest (Fig. 10 a). The isotactic polymers may be stabilized by assuming the helix conformation reported for isotactic poly(methyl methacrylate)401. Nucleic add bases are situated outside the polymer chain so that they can form the complex, although the interaction is not so strong. On the other hand, the syndiotactic polymer may have a rod-like conformation that is supported by the low solubility of the polymer and by NMR spectra321. Tlierefoie, it is well understood that the complex formation ability of the syndiotactic polymers is very low. 

Zambelli et al. reported on the mechanism of styrene polymerization [36]. They showed that the main chain of the syndiotactic polymer has a statistically trans-trans conformation. It was established then the double-bond opening mechanism in the syndiospecific polymerization of styrene involves a cis opening. The details in the control of the monomer coordination for this polymerization mechanism were examined by Newman and Malanga using detailed, 3C NMR. It was shown through the analysis of tacticity error (rmrr) that the tacticity in the polymer is chain-end controlled and that the last monomer added directs the orientation and coordination of the incoming monomer unit prior to insertion [37]. 

Fig. 4-1. (a) Isoiactic polymer in a planar zigzag conformation, (b) Syndiotactic polymer in a planar zigzag confoniiation. 

Sundararajan has studied silane polymers including polymethylphenyl-silylene)243 and polysilapropylene. " " Different tacticities and conformations of polymethylphenylsilylene were examined and the relative stabilities of each were reported. The most stable configuration was for the syndiotactic polymer with an all-trans conformation. Helix parameters, a priori bond probability, and characteristic ratios were calculated for this polymer. Polysilapropylene was studied in a similar manner. MM2 energies of the minimum for each of the different rotational isomers were included. As with the first study, contour plots of both energy and helix parameters versus (j) and < ) + 1 angles were given. 

An isotactic structure is one in which the optically active centers of the repeat units all have the same absolute stereochemistry (G. Natta, P. Pino, P. Corradini, F. Danusso, E. Mantica, G. Mazzanti, G. Moraglio, J. Am. Chem. Soc. 1955, 77, 1708) in a syndiotactic polymer, neighboring units have opposite stereochemistry. If an isotactic polyolefin is drawn in its extended conformation, it will have all its substituents pointing in the same direction. If an isotactic polyketone is drawn in its extended conformation, the substituents will alternately point up and down. 

Perhaps the most enlightening work in this area has been carried out by Schulz and his co-workers.With Na" " counterion in THF one-ended living polymer yields a predominantly syndiotactic product, conforming to the anticipated statistical theory. Furthermore, the kinetic data obtained in the presence of excess of Na+BPh4 are sufficiently detailed and precise for the... 

Raman spectroscopy is sensitive to polymer conformation. For example, a polymer blend of polybutadiene-polystyrene in which polybutadiene is used to increase toughness of the polystyrene can be examined by Raman microscopy to identify its heterogeneity. Polybutadiene has three isomer conformations (cis-1,4, trans-1,4 and syndiotactic-1,2). These three types of isomers can be identified from C=C stretching modes as shown in Figure 9.36. The Raman spectra of the copolymer indicate the difference in amounts of isomer types at the edge and the center of the polybutadiene-polystyrene sample. Relative amounts of these isomer types affect the mechanical properties of the copolymer. 

A similar situation is encountered in the case of syndiotactic polymers. Here the conformation required is that successive substituents are located on opposi sides of the chain ... 

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