In this paper

we review our recent progress in the synthesis and application of styryl-capped polypropylene (PP-

t

-St)

an excellent reactive polyolefin that is both convenient and efficient in synthesis and facile and versatile in application for preparing advanced polypropylene materials

via

macromolecular engineering. The synthesis of PP-

t

-St is made possible by a unique chain transfer reaction coordinated by a bis-styrenic molecule

such as 1

4-divinylbenzene (DVB) and 1

2-bis(4-vinylphenyl)ethane (BVPE)

and hydrogen in typical

C

2

-symmetric metallocene (

e.g. rac

-Me

2

Si(2-Me-4-Ph-Ind)

2

ZrCl

2

in association with methylaluminocene

MAO) catalyzed propylene polymerization. The regio-selective 2

1- insertion of the styrenic double bond in DVB or BVPE into the overwhelmingly 1

2-fashioned Zr-PP propagating chain enables substantial dormancy of the catalyst active site

which triggers selective hydrogen chain transfer that

with the formed Zr-H species ultimately saturated by the insertion of propylene monomer

results in an exclusive capping of the afforded PP chains by styryl group at the termination end. With a highly reactive styryl group at chain end

PP-

t

-St has been used as a facile building block in PP macromolecular engineering together with the employment of state-of-the-art synthetic polymer chemistry to fabricate broad types of new polypropylene architectures.