The copolymerization of myrcene with ethylene and propylene using half-sandwich scandium complexes bearing various auxiliary ligands has been examined. In the copolymerization of myrcene with ethylene, the THF-free aminobenzyl scandium complex bearing a relatively small cyclopentadienyl ligand (C₅H₅)Sc(CH₂C₆H₄NMe₂-o)₂ (1) afforded diblock myrcene–ethylene copolymers with a high myrcene content and predominant cis-1,4-structure, whereas the analogous scandium complex with a larger cyclopentadienyl ligand (C₅Me₄SiMe₃)Sc(CH₂C₆H₄NMe₂-o)₂ (2) afforded multiblock myrcene–ethylene copolymers with different myrcene contents and a predominant 3,4-structure. In contrast, the THF-containing trimethylsilylmethyl scandium complex (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂(THF) (3) afforded alternating myrcene–ethylene copolymers on using a sufficient amount of myrcene. More remarkably, the terpolymerization of myrcene with ethylene and propylene has also been realized using a scandium complex 3, yielding a new family of myrcene-based ethylene–propylene–diene rubbers (EPDM) with versatile CC double bonds in the main and side chains. By efficiently transforming the CC double bonds of the resulting myrcene-based EPDM into other polar groups, versatile functionalized polyolefins such as thioacetic acid, sulfoacid, and epoxidized, hydroxylated–chlorinated and furan functionalized polyolefins were obtained.

By using an alkylaluminium catalyst system i-Bu₃Al/H₃PO₄/1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), the random copolymerization and terpolymerization of furfuryl glycidyl ether (FGE) with epichlorohydrin (ECH) and ethylene oxide (EO) have been achieved for the first time to afford a new family of furan functionalized polyepichlorohydrin elastomers. The composition of the obtained FGE/ECH copolymers, FGE/EO copolymers and FGE/ECH/EO terpolymers coincided with the co-monomer feed ratio, and furan groups could be quantitatively and randomly incorporated into polyepichlorohydrin elastomers. Based on the Diels–Alder (DA) reaction of furan functionalized polyepichlorohydrin elastomers and 4,4′-methylenebis(N-phenylmaleimide), a new series of thermoreversible cross-linked polyepichlorohydrin elastomers was successfully synthesized. These thermoreversible DA cross-linked polyepichlorohydrin elastomers possess mechanical properties that can be tuned by adjusting the content of FGE units in the FGE/ECH/EO terpolymers. The mechanical properties of DA cross-linked polyepichlorohydrin elastomers were significantly better than those of traditional vulcanized polyepichlorohydrin elastomers, and they could be used as a structural material without reinforcing agents. More importantly, the DA cross-linked polyepichlorohydrin elastomers could be remolded and self-healed without loss of performance.

Amino-functionalized crystalline styrenic thermoplastic elastomers were prepared by carrying out stereoselective copolymerizations of 4-(N,N-diphenylamino)styrene and isoprene with the use of a C₅H₅-ligated scandium catalyst.