Polyolefins account for almost half of the 300 million tons of polymers produced annually. This strong market penetration comes from a combination of inexpensive monomers, extremely efficient polymerization processes, and excellent mechanical properties. Despite these great characteristics the incorporation of polar functionalities are highly desired as this would extend the range of applications of these materials by modifying surface and interfacial properties. Block copolymers containing polyolefin and polar segments are among the most desirable due to the high tunability of their chemical structure (morphology, architecture, and domain size). However, due to the high oxophilicity of the insertion metal catalysts used in industry, commercial polyolefin block copolymers have been limited to non-polar monomers.<br/>Here we develop two approaches to produce polyolefins (HDPE, LLDPE and PP) block copolymers with series of catalytic reactions. Cross metathesis or tandem hydroformylation/hydrogenation are the key reactions enabling the formation of block copolymers. These methodologies can quantitatively transform primary, secondary and tertiary olefins to access common controlled polymerizations (ROP, anionic, or ATRP) with no homopolymer formation. The catalytic nature of these polymerizations enable high and large scale synthesis. Additionally, the range of monomers accessible by controlled polymerizations makes this system a powerful platform to generate a wide range of polyolefin containing materials.

Catalytic incorporation of polyolefins into functionalized (polar and non-polar) block copolymers

2019 Fall National Meeting

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