Polyethylene materials with in-chain ketones from nonalternating catalytic copolymerization

Baur, Maximilian; Lin, Fei; Morgen, Tobias O.; Odenwald, Lukas; Mecking, Stefan

doi:10.1126/science.abi8183

Cited by 133 publications

(181 citation statements)

References 46 publications

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“…Subsequent reaction with NaH afforded the desired nickel complex ( Ni-ONa ) in near-quantitative yield. Inspired by Mecking and coworkers’ recent works on perfluorophenyl-substituted phosphinophenolate nickel catalyst 11 , the corresponding OH and ONa tagged nickel catalysts ( Ni-F-OH and Ni-F-ONa ) were also prepared. 1 H NMR characterization showed the coexistence of Ni- Me and Ar- OH signals in both Ni-OH and Ni-F-OH , and the integration of Ni- Me signal matched very well with the rest of the ligand signals (Supplementary Fig.…”

Section: Resultsmentioning

confidence: 99%

“…Industrially successful early transition-metal catalysts cannot perform such tasks due to the poisoning effects of polar groups towards metal centers. Within this context, late-transition-metal-based olefin polymerization catalysts have received continuous interest because of their low oxophilicity and correspondingly high tolerance towards polar groups 11 – 18 .…”

Section: Introductionmentioning

confidence: 99%

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A general strategy for heterogenizing olefin polymerization catalysts and the synthesis of polyolefins and composites

Zou

Chen

2022

Nat Commun

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The heterogenization of homogeneous metal complexes on solid supports presents an efficient strategy for bridging homogeneous catalysts with industrially-preferred heterogeneous catalysts; however, a series of drawbacks restrict their implementation in olefin polymerization, particularly for copolymerization with polar comonomers. In this contribution, we report an ionic anchoring strategy that is highly versatile, generally applicable to different systems, and enables strong catalyst-support interactions while tolerating various polar functional groups. In addition to greatly enhanced polymerization properties, the supported catalysts achieved higher comonomer incorporation than their unsupported counterparts. This strategy enabled efficient polymerization at high temperatures at large scale and great control over product morphology, and the facile synthesis of polyolefin composites. More importantly, the dispersion of different fillers in the polyolefin matrix produced great material properties even at low composite loadings. It is expected that this strategy will find applications in different catalytic systems and the synthesis of advanced engineering materials.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A general strategy for heterogenizing olefin polymerization catalysts and the synthesis of polyolefins and composites

Zou

Chen

2022

Nat Commun

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“…Given that the xenon lamp (covering the wavelength of sunlight) was not as effective as the 275 nm UV light for the copolymer degradation, the material may be decomposed on-demand upon UV irradiation. It should be noted that during our study, new catalysts 4a and 5a were developed by Chen 10 ) and Mecking 11 ) independently, for lowering the content of the alternating structure in the ethylene/CO copolymers. Mecking reported that the mechanical property, the stress–strain curves, of the ketone-containing polyethylene (0.6 mol% of CO) is also similar to that of polyethylene.…”

Section: C1 Comonomersmentioning

confidence: 94%

Copolymerization of ethylene with non-vinyl polar monomers

Nozaki

2022

Proceedings of the Japan Academy. Ser. B: Physical and Biologic

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Introduction of functional groups on polyethylene endows it with a higher surface property and thus various catalysts have been developed for the copolymerization of ethylene with polar vinyl monomers. Aside from vinyl monomers, however, other classes of polar monomers have not found application in the copolymerization with ethylene. Here, in this short review article, our latest studies on catalyst development aiming at the use of non-vinyl polar monomers and the properties of the resulting copolymers are summarized.

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“…[335] In recent advances, nickel and palladium catalysts were successfully tailored to enable random incorporation of small amounts of carbon monoxide into PE chains. [336,337] High-molar-mass PE containing few isolated in-chain ketone groups is rendered photodegradable without adversely affecting PE-like processing or property profiles. More research is needed to clarify the fate of the resulting photodegraded PE fragments in the environment.…”

Section: Oxo-and Photodegradationmentioning

confidence: 99%

Closing the Carbon Loop in the Circular Plastics Economy

Schirmeister

Mülhaupt

2022

Macromol. Rapid Commun.

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Today, plastics are ubiquitous in everyday life, problem solvers of modern technologies, and crucial for sustainable development. Yet the surge in global demand for plastics of the growing world population has triggered a tidal wave of plastic debris in the environment. Moving from a linear to a zero‐waste and carbon‐neutral circular plastic economy is vital for the future of the planet. Taming the plastic waste flood requires closing the carbon loop through plastic reuse, mechanical and molecular recycling, carbon capture, and use of the greenhouse gas carbon dioxide. In the quest for eco‐friendly products, plastics do not need to be reinvented but tuned for reuse and recycling. Their full potential must be exploited regarding energy, resource, and eco‐efficiency, waste prevention, circular economy, climate change mitigation, and lowering environmental pollution. Biodegradation holds promise for composting and bio‐feedstock recovery, but it is neither the Holy Grail of circular plastics economy nor a panacea for plastic littering. As an alternative to mechanical downcycling, molecular recycling enables both closed‐loop recovery of virgin plastics and open‐loop valorization, producing hydrogen, fuels, refinery feeds, lubricants, chemicals, and carbonaceous materials. Closing the carbon loop does not create a Perpetuum Mobile and requires renewable energy to achieve sustainability.

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Polyethylene materials with in-chain ketones from nonalternating catalytic copolymerization

Cited by 133 publications

References 46 publications

A general strategy for heterogenizing olefin polymerization catalysts and the synthesis of polyolefins and composites

A general strategy for heterogenizing olefin polymerization catalysts and the synthesis of polyolefins and composites

Copolymerization of ethylene with non-vinyl polar monomers

Closing the Carbon Loop in the Circular Plastics Economy

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