Abstract
AbstractThis brief account discusses the development of HCl/TiCl4‐n(OR)n (n = 1–4), the titanium‐based new initiating systems for living cationic polymerizations of vinyl ethers and styrene. The focus of this development is controlling the Lewis acidity of the metal halide components [TiCl4‐n(OR)n] or “activators” in relation to the structure of the monomers. Thus, for vinyl ethers, relatively mild Lewis acids such as TiCl(OiPr)3 and TiCl2(OiPr)2 are effective, whereas for styrene, a stronger Lewis acid such as TiCl3(OiPr) is employed along with an added salt (nBu4N+Cl−). In both cases, living polymers of controlled molecular weights can be obtained in methylene chloride solvent at −15°C.
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