Efficient Synthesis of Polar Functionalized Polyolefins with High Biomass Content

Introducing polar biomass groups into polyolefins can not only improve their nonpolar nature but also conform to the concept of sustainable development. Now, an efficient route to generate polar functionalized polyolefins with high biomass content is reported. Two kinds of bioresourced comonomers are designed by assembling biomass groups (oleyl and cinnamyl groups) with the norbornene structure and inserted into the polyolefins by phosphine-sulfonate palladium-catalyzed copolymerization reactions. The norbornene spacer in the comonomers leads to great ethylene copolymerization results of catalytic activities (3.3 × 105 to 2.04 × 106 g mol–1 h–1), polymer molecular weights (68,000–188,000 g mol–1), and comonomer incorporations (1.9–22.4 mol %). Meanwhile, the insertions of these comonomers can easily tune the various properties of polyolefin materials, such as thermal, mechanic, surface, and optical properties. Furthermore, the deliberately introduced internal carbon–carbon double bonds in the biomass groups provide further reactive sites for sulfur vulcanization to enhance the tensile strength of copolymers. Two kinds of reversible dynamic cross-linked networks can also be built based on these carbon–carbon double bonds and endow the obtained polymers with good remodeling performances.