Cationic Polymerization of Cyclic Dienes. IX. The Structure of Poly(1,3-cyclohexadiene) and Poly(cis, cis-1,3-cycloöctadiene)

Synthesis of star poly(1,3‐cyclohexadiene): Grafting reaction of poly(1,3‐cyclohexadienyl)lithium onto C60

“…Poly(1,3-cyclohexadiene) (PCHD), which has a special structure of directly connected six-membered rings in the main chain, has been recognized since the 1950s as an attractive precursor for the synthesis of a new class of high performance polymers. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] However, the difficulty of PCHD polymerization has been a major and serious problem that has prevented progress in the study of PCHDs. The polymers obtained under various conditions were usually of low molecular weight or in low yield, and the microstructure of the polymer chain could not be controlled.…”

“…[1][2][3][4][5][6][7][8][9][10]13,14 The most important challenge was to improve the polymerization reaction of 1,3-cyclohexadiene (1,3-CHD), so that a variety of different approaches have been attempted. [1][2][3][4][5][6][7][8][9][10]13,14 In previous articles, [17][18][19][20] we reported the first successful example of controlled polymerization of 1,3-CHD, and the polymer chain structure of PCHD was strongly affected by the type and amount of amine used, and also by the use of alkyllithium as an initiator. 19,20 In addition, it was concluded that the most convenient route to synthesize the controlled PCHD was the (living) anionic polymerization of 1,3-CHD.…”

“…Of particular interest regarding the polymer chain structure of PCHDs is the study of François and co-workers, 34 which reported a star-shaped polystyrene (PSt)-PCHD block copolymer with a fullerene-C 60 (C 60 ) core. C 60 (PSt-PCHD) 6 and C 60 (St-PCHD-PSt) 6 were successfully synthesized using the controlled grafting reaction of polystyryllithium (PStLi) onto C 60 , which was discovered by Ederlé and Mathis. 37 The synthesis of C 60 (PCHD-PSt) n was then attempted using the grafting reaction of PSt-poly(1,3-cyclohexadienyl)lithium (PSt-PCHDLi) onto C 60 .…”