AbstractThe effects of heat treatment below the melting point of 3,9‐bis{1,1‐dimethyl‐2[β‐(3‐tert‐butyl‐4‐hydroxy‐5‐methylphenyl)propionyloxy]ethyl}‐2,4,8,10‐tetraoxaspiro[5,5]‐undecane (AO‐80) on the thermal and dynamic mechanical properties and microstructure of chlorinated polyethylene (CPE) filled with vitrified AO‐80 particles were investigated. The initial AO‐80 was a complete crystal, whereas AO‐80 obtained by cooling from its melting state was amorphous. The vitrified AO‐80 particles could crystallize again in a CPE matrix by an annealing treatment, but this crystal was different from the initial AO‐80 in the microstructure. In addition, the incorporation of CPE chains caused a dramatic increase in the modulus. As a result, the AO‐80 crystal particles that contained some CPE chains acted as multifunctional crosslinks, and the CPE/AO‐80 hybrid was found to be a new type of elastomer. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 209–215, 2004