Inclusion polymerization of 1‐chlorobutadiene was studied using 3α,12α‐dihydroxy‐5β‐cholan‐24‐oic acid (deoxycholic acid, DCA) as host molecules. It was found that the poly(1‐chlorobutadiene) had almost 100% of head to tail, trans‐1,4‐structure on the basis of 13C‐NMR and IR spectroscopies. This was the first example of preparing the highly regulated poly(1‐chlorobutadiene) by using the inclusion polymerization technique. The polymers obtained were optically active and the maximum value of specific rotation was [α]D‐41.9°. Both the rate constants and the value of activation energy of the elementary reactions of inclusion polymerization of 1‐chlorobutadiene were determined by graphical evaluation. The activation energy of propagation and termination was 11.7 and 11.1 kcal/mol, respectively.
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