RESUMEN

Water-soluble [P,O]Ni(II) catalysts enable the direct catalytic nonalternating copolymerization of fundamental comonomers ethylene and carbon monoxide (CO) in water as an environmentally friendly reaction medium. This yields stable aqueous dispersions of high molecular weight polyethylene containing ∼1 mol % of largely isolated in-chain keto groups in the form of particles with sizes between 100 nm and 1 µm. The intermediate species of chain growth resulting from incorporation of polar comonomers are amenable to specific chain termination pathways in conjunction with water.

RESUMEN

Recent advances in Ni(II) catalyzed, nonalternating catalytic copolymerization of ethylene with carbon monoxide (CO) enable the synthesis of in-chain keto-functionalized polyethylenes (keto-PEs) with high-density polyethylene-like materials properties. Addition of norbornene as a bulky, noncrystallizable comonomer during catalytic polymerization allows tuning of the crystallinity in these keto-PE materials by randomly incorporated norbornene units in the polymer chain, while molecular weights are not adversely affected. Such crystallinity-reduced keto-PEs are characterized as softer materials with better ductility and may therefore be more suited for, e.g., potential film applications.

RESUMEN

Polyethylene deconstruction to reusable smaller molecules is hindered by the chemical inertness of its hydrocarbon chains. Pyrolysis and related approaches commonly require high temperatures, are energy-intensive, and yield mixtures of multiple classes of compounds. Selective cleavage reactions under mild conditions (

RESUMEN

Polyethylenes endowed with low densities of in-chain hydrolyzable and photocleavable groups can improve their circularity and potentially reduce their environmental persistency. We show with model polymers derived from acyclic diene metathesis polymerization that the simultaneous presence of both groups has no adverse effect on the polyethylene crystal structure and thermal properties. Post-polymerization Baeyer-Villiger oxidation of keto-polyethylenes from non-alternating catalytic ethylene-CO chain growth copolymerization yield high molecular weight in-chain keto-ester polyethylenes (Mn ≈50.000 g mol-1 ). Oxidation can proceed without chain scission and consequently the desirable materials properties of HDPE are retained. At the same time we demonstrate the suitability of the in-chain ester groups for chemical recycling by methanolysis, and show that photolytic degradation by extended exposure to simulated sunlight occurs via the keto groups.

RESUMEN

Linear polyethylenes with a combination of incorporated in-chain keto as well as side-chain ester groups are formed by Ni(II)-catalyzed terpolymerization of ethylene, carbon monoxide, and methyl acrylate. These possess a random structure, with largely isolated nonalternating in-chain keto groups as well as ester-substituted units adjacent to the polyethylene chain, whereas the solid-state structure of polyethylene is retained. Molecular weights of the terpolymers (Mn ∼ 20.000 g mol-1) are predominantly determined by chain transfer after acrylate incorporation.

Asunto(s)

Monóxido de Carbono , Polietileno , Acrilatos/química , Catálisis , Ésteres , Etilenos

RESUMEN

Polyethylene materials with in-chain-incorporated keto groups were recently enabled by nonalternating copolymerization of ethylene with carbon monoxide in the presence of Ni(II) phosphinephenolate catalysts. We elucidate the mechanism of this long-sought-for reaction by a combined theoretical DFT study of catalytically active species and the experimental study of polymer microstructures formed in pressure-reactor copolymerizations with different catalysts. The pathway leading to the desired nonalternating incorporation proceeds via the cis/trans isomerization of an alkyl-olefin intermediate as the rate-determining step. The formation of alternating motifs is determined by the barrier for the opening of the six-membered C,O-chelate by ethylene binding as the decisive step. An η2-coordination of a P-bound aromatic moiety axially oriented to the metal center is a crucial feature of these Ni(II) catalysts, which also modulates the competition between the two pathways. The conformational constraints imposed in a 2',6'-dimethoxybiphenyl moiety overall result in a desirable combination of disfavoring ethylene coordination along the alternating incorporation pathway, which is primarily governed by electronics, while not overly penalizing the nonalternating chain growth, which is primarily governed by sterics.

RESUMEN

The world's most abundantly manufactured plastic, polyethylene, consists of inert hydrocarbon chains. The introduction of reactive polar groups in these chains could help overcome problematic environmental persistence and enhance compatibility with other materials. We show that phosphinophenolate-coordinated nickel complexes can catalyze nonalternating copolymerization of ethylene with carbon monoxide to incorporate a low density of individual in-chain keto groups in polyethylene chains with high molecular weight while retaining desirable material properties. After processing by conventional injection molding techniques, tensile properties remain on par with those of standard high-density polyethylene while also imparting photodegradability.

RESUMEN

Small amounts of in-chain keto groups render polyethylene (PE) photodegradable, a desirable feature in view of environmental plastics pollution. Free-radical copolymerization of CO and ethylene is challenging due to the formation of stable acyl radicals which hinders further chain growth. Here, we report that copolymerization to polyethylenes with desirable low ketone content is enabled in dimethyl carbonate organic solvent or under aqueous conditions at comparatively moderate pressures <350 atm that compare favorable to typical ethylene polymerization at 2000 atm. Hereby, thermoplastic processable materials can be obtained as demonstrated by injection molding and tensile testing. Colloidally stable dipersions from aqueous polymerizations form continuous thin films upon drying at ambient conditions. Extensive spectroscopic investigation including 13C labeling provides an understanding of the branching microstructures associated with keto groups. Exposure of injection molded materials or thin films to simulated sunlight under sea-like conditions results in photodegradation.