Synthesis of novel hydrocarbon polymers containing 6-membered rings in the main chain: living anionic polymerization of 1,3-cyclohexadiene

The n-butyllithium (n-BuLi)/N,N,N',N'-tetrametylethylene-diamine (TMEDA) system (the molar ratio of TMEDA to n-BuLi higher than 4/4) has been found to polymerize 1,3-cyclohexadiene (1,3-CHD) to produce “living” polymer having narrow molecular weight distribution with well-controlled polymer chain length. Binary and ternary block copolymers with narrow molecular weight distribution could be synthesized from 1,3-cyclohexadiene, styrene, and butadiene with very high efficiency. These polymers and their hydrogenated derivatives have excellent thermal, mechanical, chemical, and optical properties for the new industrial materials.