Isotactic structures energy calculations

Isotactic poly(methyl methacrylate), also, is an intricate case, resolved only after a 20-year debate. The repetition period along the chain axis is 10.40 A corresponding to S monomer units the entire cell contains 20 monomer units (four chains). At first, the stmcture was resolved as a 5/1 helix (183) with = 180° and 62 — 108° but no reasonable packing was found using this assumption. Further conformational calculations showed that helices like 10/1 or 12/1 should be more stable than the 5/1 helix. The structure was solved by Tadokoro and co-workers (153b) who proposed the presence of a double helix. Two chains, with the same helical sense and the same direction but displaced by 10.40 A one from the other are wound on each other, each chain having 10 monomer units per turn [i(10/l)] and a 20.80-A repeat period. As a result, the double helix has a 10.40-A translational identity period, identical to that found in the fiber spectmm. The conformational parameters are Of = 179° and 2 = -148°. Energy calculations indicate that the double helix is more stable by 4.4 kcal per-mole of monomer units than two isolated 10/1 helices, a result that is in line with the well-known capacity of this polymer to form complexes in solution (184). 

A RIS model with neighbor interactions is used to calculate mean-square unperturbed dimensions and dipole moments for vinyl chloride chains having degrees of polymerization ranging from x = 1 to 1 50 and stereochemical structures ranging from perfect syndiotacticity to perfect isotacticity. Conformational energies used in these calculations are those which have been established in the analysis based on the stereochemical equilibration of 2,4-dichloro-n-pentane by Flory and Williams (A 002). 

The intramolecular interaction energy was calculated for five isotactic polymers, namely, isotactic polypropylene, poly(U-methyl-l-pentene), poly(3-methyl-1-butene), polyacetaldehyde, and poly(methyl methacrylate) (23). The molecular structures of the first four polymers have already been determined by x-ray analyses as (3/1) (2k), (7/2) (18,25.,26), (U/l) (21), and (U/l) helices (28), respectively. Here (7/2) means seven monomeric units turn twice in the fiber identity period. For isotactic poly(methyl methacrylate) (29), a (5/l) helix was considered reasonable at the time of the energy calculation in 1970, before the discovering of... 

Ferro, D. R., Bruckner, S., Meille, S. V. and Ragazzi, M. (1992). Energy calculations for isotactic polypropylene—a comparison between models of the alpha-crystalline and gamma-crystalline structures. Macromolecules, 25, 5231-5. [182]... 

Molecular mechanics techniques are employed to calculate the molecular structure and conformational energies of model compounds for polyphenylmethylsllylene and polysilastyrene. In both isotactic and syndiotactic stereochemical forms. The structural and conformational energy data provided are used to calculate, by application of the RIS theory, the unperturbed chain dimensions, given as the characteristic ratio, and its temperature coefficient. 

Fig. 4.14 A comparison of the observed powder ring profile for isotactic 1,4-c/s-poly(2-methyl-1,3-pentadiene) with that calculated from the structure with minimum energy (a) the observed profile and (b) the calculated profile, with peaks broadened to give the best fit. (Reprinted with permission from the American Chemical Society.)...

MM calculations with full geometry optimization have been carried out to calculate the molecular structure and conformational energies od, ..modeJ -.cpmpounds for poly (phenylmethylsilylene) [-SiPhMe-] and poly(silastyrene) [-SiPhH-SiH2-]. In each case the calculations considered both the isotactic and syndiotactic stereochemical isomeric forms of the model compounds. The structures considered are illustrated in Figures 6 and 7. 

While the exact solution of the chain structure of polystyrene in the crystalline gels would require more accurate energy minimizations in respect to all the internal coordinates (f.i. preliminary calculation show that the benzene rings are better energetically when not exactly staggered) and a comparison of calculated and observed X-ray data, the discussion above shows that a very elongated chain conformation can be built up for isotactic polystyrene. 

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