Convenient Syntheses and Versatile Functionalizations of Isotactic Polypropylene Containing Plentiful Pendant Styrene Groups with High Efficiency

Reported herein is the excellent example of regio-/stereoselective coordination copolymerization of propylene with p-(3-butenyl)styrene (BSt) which produces exclusively high molecular weight (Mw > 50 x 10(3)) isotactic polypropylenes (iPPs) with abundant ethenylbenzene (styrene) groups (>5 mol %) by use of non-metallocene catalyst. The current (pyridylamido)Hf/[Ph3C][B(C6F5)(4)]/(AlBu3)-Bu-i system, which exhibits overwhelmingly favorable reactivity toward alpha-olefin over styrene moieties, effectively promoted the copolymerization of propylene with BSt under judiciously chosen reaction conditions, in which catalytic activity (1.35 kg polymer/(mmol (Hf) h), molecular weight (M-w = 102 x 10(3)), styrene group content (8.31 mol %), and tacticity ([mmmm] > 99%) reached a satisfying level simultaneously for the first time. Side group functionalized iPPs were synthesized in an almost quantitative way via the UV-light-initiated thiol-ene click chemistry and iodine-catalyzed hydroalkylation reaction of the resultant propylene/BSt copolymer with commercially available materials, demonstrating that the propylene copolymers containing abundant pendant styrene groups are excellent reactive intermediates for the preparation of various functional iPP materials.