Precise synthesis of thermoreversible block copolymers containing reactive furfuryl groups via living anionic polymerization: the countercation effect on block copolymerization behavior

The anionic block copolymerization of 4,4'-vinylphenyl-N, N-bis(4-tert-butylphenyl) benzenamine (A) with furfuryl isocyanate (B) was carried out using potassium naphthalenide (K-Naph) in tetrahydrofuran at -78 and -98 degrees C to prepare well-defined block copolymers containing furan groups for the formation of thermoreversible networks via a Diels-Alder (DA) reaction. While no block copolymerization was observed in the absence of sodium tetraphenylborate (NaBPh4) due to side reactions, well-defined poly( B-b-A-b-B) (PBAB) copolymers with controlled molecular weights (M-n = 18 700-19 500 g mol(-1)) and narrow molecular weight distributions (M-w/M-n = 1.08-1.17) were successfully synthesized in the presence of excess NaBPh4. The occurrence of the undesirable side reactions during polymerization of B was effectively prevented by NaBPh4, which results in the change in the countercation from K+ to Na+ for further polymerization of B. The cross-linking via the DA reaction between the furan groups of PBAB and bismaleimide was proved by FT-IR and differential scanning calorimetry (DSC), and the thermoreversible properties of the cross-linked polymer were subsequently investigated using DSC and solubility testing.