Some cis‐ and trans‐β‐chlorovinyl alkyl ethers were polymerized in a stereospecific way, and crystalline polymers. The steric structures of poly(cis‐) and poly(trans‐β‐chloro vinyl butyl ethers) are different one from another, and more precisely of the erythro and threo di‐isotactic type respectively. These results demonstrate a steric polymerization mechanism, which is identical in both forms, with a cis opening of the double bond. Moreover some aspects of the stereospecific polymerization mechanism of mono‐olefinic monomers are discussed. Beside the type of opening of the double bond (cis or trans), determining the steric ratios inside each monomeric unit, also the mode of attack of the monomer to the chain is considered here. It can take place on one or on the other of the two enantiomer faces (D or L) of the monomer in a constant or in an alternated way. Such a steric attack determines the structural relationships between subsequent monomeric units.
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Natta et al. (1962) studied this question.