The product from free radical and coordination polymerization generally are homopolymer or random copolymer with broad molecular weight distribution.In the past two decades

the breakthroughs in controlled/living radical and coordination polymerization and shuttling polymerization make it possible to use almost all vinyl monomers

particularly those cheap monomers

to produce more complex chain structures like di-

tri-block copolymer and gradient copolymers.With rational design

these copolymers might be high performance and high added value synthetic materials.The mechanisms and the up-to-date progress of these polymerization methods were introduced

and their possible applications were discussed.