Crystalline sulfur-functionalized poly(α-olefin) synthesized by scandium-catalyzed coordination polymerization

Abstract

Sulfur-functionalized poly(α-olefin) is an excellent building block for constructing topological and functional polymers but it has been utilized as an amorphous material up to now. Through a fundamental structure/property study that reveals the intriguing effects of the steric hindrance/electronic properties of the monomer, the spacer length between the sulfur atom and olefin group, and the stereoselectivity of the polymerization process on the crystalline performance of sulfur-functionalized poly(α-olefin), the first crystalline sulfur-functionalized poly(α-olefin) is reported. Combined with organoborate, an N-heterocyclic carbene ligated scandium trialkyl complex catalyzed monomers to produce a series of syndiotactic sulfur-functionalized poly(α-olefin)s (rrrr up to 0.95) which formed crystalline materials with a T_m of up to 91 °C.