Star‐shaped, star‐block‐linear, and hyperbranched poly(1,3‐cyclohexadiene) (PCHD) (co)polymers were synthesized through a convergent living anionic polymerization process or via addition of divinylbenzene. Chemical modification of star‐shaped PCHDs, including aromatization, hydrogenation, fluorination, and sulfonation, was carried out in order to manipulate the physical and thermal properties of these materials. The obtained (co)polymers were characterized by gel permeation chromatography, 1H NMR, DSC, and thermal gravimetric analysis in order to elucidate their molecular weights, molecular weight distributions, chemical nature, and physical and thermal properties. The synthetic approaches described herein offer routes to novel structure and functionality in PCHD‐based materials.magnified image
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