Functional Polyethylenes by Organometallic-Mediated Radical Polymerization of Biobased Carbonates

Abstract

Partly or fully renewable (co)­polymers are gaining interest in both academia and industry. Polyethylene is a widely used polymer, classically derived from fossil fuels, with a high versatility stemming from the introduction of comonomers altering the mechanical properties. The introduction of renewable functionalities into this polymer is highly attractive to obtain functional, tunable, and at least partially renewable polyethylenes. We herein report the introduction of biosourced cyclic carbonates into polyethylene using organometallic-mediated radical polymerization under mild conditions. Molecular weights of up to 14 600 g mol–1 with dispersities as low as 1.19 were obtained, and the cyclic carbonate content could be easily tuned by the ethylene pressure during the polymerization. As a proof of concept, the hydrolysis of the cyclic carbonates of a representative copolymer was explored, and it provided polyethylene-bearing vicinal diols, with a hydrolysis degree of 71%. Given the multitude of chemoselective modifications possible on cyclic carbonates as well as the fact that many allylic- and alkylidene-type cyclic carbonates are accessible from renewable resources, this work opens up an avenue for the design of functional and more sustainable polyethylenes.

Synthesis of Degradable Polyethylene and Poly(ethylene-co-vinyl acetate) by Radical Co- and Terpolymerization of Ethylene, ε-Thionocaprolactone, and Vinyl Acetate

“…The choice of these starting conditions was dictated by our previous works dealing with RDRP of ethylene 32−34 and the fact that DMC was shown to induce less transfer reaction than other candidates. The experiments were monitored by 1 H NMR spectroscopy analyses of the polymerization medium over 180 min, with each experiment representing one polymerization time (Figure S1).…”

“…f Determined by SEC-THF, using polystyrene as standards. g Determined by 1 H NMR of terpolymer, following eq S6. h No TCL was used.…”

“…The terpolymers were analyzed by 1 H NMR (Figures S17− S20). As for the P(E-co-TCL) copolymers, the new triplets appearing at 2.8 and 2.5 ppm were assigned to the signal of the opened form of the TCL inserted unit, while a broad peak at 3.5 ppm was assigned to the closed form.…”

Synthesis of Degradable Polyethylene and Poly(ethylene-co-vinyl acetate) by Radical Co- and Terpolymerization of Ethylene, ε-Thionocaprolactone, and Vinyl Acetate

“…The choice of these starting conditions was dictated by our previous works dealing with RDRP of ethylene 32−34 and the fact that DMC was shown to induce less transfer reaction than other candidates. The experiments were monitored by 1 H NMR spectroscopy analyses of the polymerization medium over 180 min, with each experiment representing one polymerization time (Figure S1).…”

“…f Determined by SEC-THF, using polystyrene as standards. g Determined by 1 H NMR of terpolymer, following eq S6. h No TCL was used.…”

“…The terpolymers were analyzed by 1 H NMR (Figures S17− S20). As for the P(E-co-TCL) copolymers, the new triplets appearing at 2.8 and 2.5 ppm were assigned to the signal of the opened form of the TCL inserted unit, while a broad peak at 3.5 ppm was assigned to the closed form.…”

Exovinylene Cyclic Carbonates: Multifaceted CO2‐Based Building Blocks for Modern Chemistry and Polymer Science

“…Under basic methanolysis, both VAc and DMACC units are hydrolyzed, leading to PVOH bearing vicinal diols. Similar procedures applied to P(E‐ co ‐DMACC) yielded polar polyethylene with vicinal diols [141] …”

CO 2 fixation: cycloaddition of CO 2 to epoxides using practical metal-free recyclable catalysts

“…His main interest is the development of realistic and affordable homogeneous and heterogeneous catalysts for small molecule activation. pendant carbonate groups [79][80][81] and for the synthesis of polymeric materials for lithium batteries. 82 Specifically, GCMA (glycerol carbonate methacrylate) has emerged as a promising sustainable CO 2 -based monomer 83 for the synthesis of polymers with applications as crosslinking agents for coatings 84 and in catalysis.…”

Synthesis of Degradable Polyethylene and Poly(ethylene-co-vinyl acetate) by Radical Co- and Terpolymerization of Ethylene, ε-Thionocaprolactone, and Vinyl Acetate

“…The choice of these starting conditions was dictated by our previous works dealing with RDRP of ethylene 32−34 and the fact that DMC was shown to induce less transfer reaction than other candidates. The experiments were monitored by 1 H NMR spectroscopy analyses of the polymerization medium over 180 min, with each experiment representing one polymerization time (Figure S1).…”

“…f Determined by SEC-THF, using polystyrene as standards. g Determined by 1 H NMR of terpolymer, following eq S6. h No TCL was used.…”

“…The terpolymers were analyzed by 1 H NMR (Figures S17− S20). As for the P(E-co-TCL) copolymers, the new triplets appearing at 2.8 and 2.5 ppm were assigned to the signal of the opened form of the TCL inserted unit, while a broad peak at 3.5 ppm was assigned to the closed form.…”

Exovinylene Cyclic Carbonates: Multifaceted CO2‐Based Building Blocks for Modern Chemistry and Polymer Science

“…Under basic methanolysis, both VAc and DMACC units are hydrolyzed, leading to PVOH bearing vicinal diols. Similar procedures applied to P(E‐ co ‐DMACC) yielded polar polyethylene with vicinal diols [141] …”

CO 2 fixation: cycloaddition of CO 2 to epoxides using practical metal-free recyclable catalysts

“…His main interest is the development of realistic and affordable homogeneous and heterogeneous catalysts for small molecule activation. pendant carbonate groups [79][80][81] and for the synthesis of polymeric materials for lithium batteries. 82 Specifically, GCMA (glycerol carbonate methacrylate) has emerged as a promising sustainable CO 2 -based monomer 83 for the synthesis of polymers with applications as crosslinking agents for coatings 84 and in catalysis.…”

Synthesis of Degradable Polyethylene and Poly(ethylene-co-vinyl acetate) by Radical Co- and Terpolymerization of Ethylene, ε-Thionocaprolactone, and Vinyl Acetate

“…The choice of these starting conditions was dictated by our previous works dealing with RDRP of ethylene 32−34 and the fact that DMC was shown to induce less transfer reaction than other candidates. The experiments were monitored by 1 H NMR spectroscopy analyses of the polymerization medium over 180 min, with each experiment representing one polymerization time (Figure S1).…”

“…f Determined by SEC-THF, using polystyrene as standards. g Determined by 1 H NMR of terpolymer, following eq S6. h No TCL was used.…”

“…The terpolymers were analyzed by 1 H NMR (Figures S17− S20). As for the P(E-co-TCL) copolymers, the new triplets appearing at 2.8 and 2.5 ppm were assigned to the signal of the opened form of the TCL inserted unit, while a broad peak at 3.5 ppm was assigned to the closed form.…”

Exovinylene Cyclic Carbonates: Multifaceted CO2‐Based Building Blocks for Modern Chemistry and Polymer Science

“…Under basic methanolysis, both VAc and DMACC units are hydrolyzed, leading to PVOH bearing vicinal diols. Similar procedures applied to P(E‐ co ‐DMACC) yielded polar polyethylene with vicinal diols [141] …”

CO 2 fixation: cycloaddition of CO 2 to epoxides using practical metal-free recyclable catalysts

“…His main interest is the development of realistic and affordable homogeneous and heterogeneous catalysts for small molecule activation. pendant carbonate groups [79][80][81] and for the synthesis of polymeric materials for lithium batteries. 82 Specifically, GCMA (glycerol carbonate methacrylate) has emerged as a promising sustainable CO 2 -based monomer 83 for the synthesis of polymers with applications as crosslinking agents for coatings 84 and in catalysis.…”