Efficient Synthesis of Polar Functionalized Polyolefins with High Biomass Content

Abstract

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 × 10 5 to 2.04 × 10 6 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.

Synthesis of partially fluorinated polyolefins via copolymerization of ethylene with fluorinated norbornene-based comonomers

“…Introducing comonomers into polyethylene deeply affects their thermal properties. 37 Usually, the melting point (T m ) of the linear polyethylene is higher than 120 °C. [38][39][40] Comparably, the T m (86.1-97.3 °C) of the resulting copolymers decreased after inserting mono-NBFn (Table 1, entries 1-5).…”

Electronic effect regulated ethylene polymerization and copolymerization of phosphorus phenol nickel catalysts

“…The incorporation of polar comonomers is expected to modify the surface properties of polyolefin materials. 17 The surface properties of the copolymer were studied by water contact angle (WCA) test (Figure 4, Table 2, entries 1-8, entries 11-14, with a dosage of 0.3%-1.9%, Figure 5, entries 1-9). In general, the higher the content of polar monomers in copolymers, the lower the WCA.…”

“…15 Therefore, the low hydrophilicity and high tolerance to polar groups of transition metal catalysts make them highly attractive candidate catalysts. [16][17][18][19] More importantly, nickel catalysts with lower prices and higher soil content have developed rapidly in the field of nickel catalyzed olefin polymerization compared to precious metal palladium catalysts. [20][21][22][23][24][25] Especially in recent years, neutral phosphorus phenol nickel catalysts with excellent polar monomer copolymerization performance have flourished.…”

Synthesis and Characterization of 4-Methyl-1-Pentene/1,5-Hexadiene Isotactic Copolymers with Enhanced Low-Temperature Mechanical Performance

“…The aim of this paper is to enchain MCP units in a controlled fashion that reduces the 4MP crystallinity, allowing a better tuning of mechanical and physical properties, without strongly affecting the glass transition temperature and transparency. Indeed, we selected this comonomeric unit since the corresponding poly­(methylene-1,3-cyclopentane) homopolymer (PMCP) has a T g of about 20 °C, similar to that of iP4MP, and also because the introduction of a cyclic group can improve the optical properties of polyolefin materials in the visible region of the electromagnetic spectrum. − Thus, this strategy allows obtaining thermoplastic materials that retain the unique properties of iP4MP but are characterized by improved toughness and deformability. Both the roles of amorphous and crystalline phases have been analyzed in detail to study the ductile behavior observed below the glass transition temperature.…”