Closed-loop recycling of polyethylene-like materials.

Plastics are key components of almost any technology today. Although their production consumes substantial feedstock resources, plastics are largely disposed of after their service life. In terms of a circular economy1-8, reuse of post-consumer sorted polymers ('mechanical recycling') is hampered by deterioration of materials performance9,10. Chemical recycling1,11 via depolymerization to monomer offers an alternative that retains high-performance properties. The linear hydrocarbon chains of polyethylene12 enable crystalline packing and provide excellent materials properties13. Their inert nature hinders chemical recycling, however, necessitating temperatures above 600 degrees Celsius and recovering ethylene with a yield of less than 10 per cent3,11,14. Here we show that renewable polycarbonates and polyesters with a low density of in-chain functional groups as break points in a polyethylene chain can be recycled chemically by solvolysis with a recovery rate of more than 96 per cent. At the same time, the break points do not disturb the crystalline polyethylene structure, and the desirable materials properties (like those of high-density polyethylene) are fully retained upon recycling. Processing can be performed by common injection moulding and the materials are well-suited for additive manufacturing, such as 3D printing. Selective removal from model polymer waste streams is possible. In our approach, the initial polymers result from polycondensation of long-chain building blocks, derived by state-of-the-art catalytic schemes from common plant oil feedstocks, or microalgae oils15. This allows closed-loop recycling of polyethylene-like materials.

Synthesis and Deconstruction of Polyethylene-type Materials.

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 (

Closed-Loop Recyclable and Nonpersistent Polyethylene-like Polyesters.

ConspectusAliphatic polyesters based on long-chain monomers were synthesized for the first time almost a century ago. In fact, Carothers' seminal observations that founded the entire field of synthetic polymer fibers were made on such a polyester sample. However, as materials, they have evolved only over the past decade. This is driven by the corresponding monomers becoming practically available from advanced catalytic conversions of plant oils, and future prospects comprise a possible generation from third-generation feedstocks, such as microalgae or waste. Long-chain polyesters such as polyester-18.18 can be considered to be polyethylene chains with a low density of potential breakpoints in the chain. These do not compromise the crystalline structure or the material properties, which resemble linear high-density polyethylene (HDPE), and the materials can also be melt processed by injection molding, film or fiber extrusion, and filament deposition in additive manufacturing. At the same time, they enable closed-loop chemical recycling via solvolysis, which is also possible in mixed waste streams containing polyolefins and even poly(ethylene terephthalate). Recovered monomers possess a quality that enables the generation of recycled polyesters with properties on par with those of the virgin material. The (bio)degradability varies enormously with the constituent monomers. Polyesters based on short-chain diols and long-chain dicarboxylates fully mineralize under industrial composting conditions, despite their HDPE-like crystallinity and hydrophobicity. Fundamental studies of the morphology and thermal behavior of these polymers revealed the location of the in-chain groups and their peculiar role in structure formation during crystallization as well as during melting. All of the concepts outlined were extended to, and elaborated on further, by analogous long-chain aliphatic polymers with other in-chain groups such as carbonates and acetals. The title materials are a potential solution for much needed circular closed-loop recyclable plastics that also as a backstop if lost to the environment will not be persistent for many decades.

Electric-Field Fluctuations as the Cause of Spectral Instabilities in Colloidal Quantum Dots.

Spectral diffusion (SD) represents a substantial obstacle toward implementation of solid-state quantum emitters as a source of indistinguishable photons. By performing high-resolution emission spectroscopy for individual colloidal quantum dots at cryogenic temperatures, we prove the causal link between the quantum-confined Stark effect and SD. Statistically analyzing the wavelength of emitted photons, we show that increasing the sensitivity of the transition energy to an applied electric field results in amplified spectral fluctuations. This relation is quantitatively fit to a straightforward model, indicating the presence of a stochastic electric field on a microscopic scale, whose standard deviation is 9 kV/cm, on average. The current method will enable the study of SD in multiple types of quantum emitters such as solid-state defects or organic lead halide perovskite quantum dots, for which spectral instability is a critical barrier for applications in quantum sensing.

Origin of Suppressed Chain Transfer in Phosphinephenolato Ni(II)-Catalyzed Ethylene Polymerization.

Recent breakthroughs in the generation of polar-functionalized and more sustainable degradable polyethylenes have been enabled by advanced phosphinephenolato Ni(II) catalysts. A key has been to overcome this type of catalysts' propensity for extensive chain transfer to enable formation of high-molecular-weight polyethylene chains. We elucidate the mechanistic origin of this paradigm shift by a combined experimental and theoretical study. Single-crystal X-ray structural analysis and cyclic voltammetry of a set of six different catalysts with variable electronics and sterics, combined with extensive pressure reactor polymerization studies, suggest that an attractive Ni-aryl interaction of a P-[2-(aryl)phenyl] is responsible for the suppression of chain transfer. This differs from the established picture of steric shielding found for other prominent late transition metal catalysts. Extensive density functional theory studies identify the relevant pathways of chain growth and chain transfer and show how this attractive interaction suppresses chain transfer.

Nopadiene: A Pinene-Derived Cyclic Diene as a Styrene Substitute for Fully Biobased Thermoplastic Elastomers.

The bicyclic 1,2-substituted, 1,3-diene monomer nopadiene (1R,5S)-2-ethenyl-6,6-dimethylbicyclo[3.1.1]hept-2-ene was successfully polymerized by anionic and catalytic polymerization. Nopadiene is produced either through a facile one-step synthesis from myrtenal via Wittig-olefination or via a scalable two-step reaction from nopol (10-hydroxymethylene-2-pinene). Both terpenoids originate from the renewable ß-pinene. The living anionic polymerization of nopadiene in apolar and polar solvents at 25 °C using organolithium initiators resulted in homopolymers with well-controlled molar masses in the range of 5.6-103.4 kg·mol-1 (SEC, PS calibration) and low dispersities (D) between 1.06 and 1.18. By means of catalytic polymerization with Me4CpSi(Me)2NtBuTiCl2 and (Flu)(Pyr)CH2Lu(CH2TMS)2(THF), the 1,4 and 3,4- microstructures of nopadiene are accessible in excellent selectivity. In pronounced contrast to other 1,3-dienes, the rigid polymers of the sterically demanding nopadiene showed an elevated glass temperature, Tg,∞ = 160 °C (in the limit of very high molar mass, Mn). ABA triblock copolymers with a central polymyrcene block and myrcene content of 60-75 mol %, with molar masses of 100-200 kg/mol were prepared by living anionic polymerization of the pinene-derivable monomers nopadiene and myrcene. This diene copolymerization resulted in thermoplastic elastomers displaying nanophase separation at different molar ratios (DSC, SAXS) and an upper service temperature about 30 K higher than that for traditional petroleum-derived styrenic thermoplastic elastomers due to the high glass temperature of polynopadiene. The materials showed good thermal stability at elevated temperatures under nitrogen (TGA), promising tensile strength and ultimate elongation of up to 1600%.

Catalytic Biorefining of Natural Oils to Basic Olefinic Building Blocks of Proven Chemical Valorization Schemes.

Catalytic transformation of renewable plant oils including microalgae and waste oil into industrially relevant α-olefins in the C3 to C10 regime is demonstrated. The biorefinery concept is comprised of a catalytic sequence of ethenolysis, double bond isomerization, and a subsequent ethenolysis, thereby cutting and rearranging the fatty acid chains into valuable chemical building blocks. A benign extraction and reaction solvent, supercritical carbon dioxide (scCO2 ), is utilized.

Degradable and Recyclable Polyesters from Multiple Chain Length Bio- and Waste-Sourceable Monomers.

Monomers sourced from waste or biomass are often mixtures of different chain lengths; e.g. catalytic oxidation of polyethylene waste yields mixtures of dicarboxylic acids (DCAs). Yet, polyesters synthesized from such monomer mixtures have rarely been studied. We report polyesters based on multiple linear aliphatic DCAs, present in chain length distributions that vary in their centers and ranges. We demonstrate that these materials can adopt high-density polyethylene-like solid state structures, and are ductile (e.g. Et 610 MPa), allowing for injection molding, or film and fiber extrusion. Melting and crystallization points of the polyesters show no odd-even effects as dipoles cannot favorably align in the crystal, similar to traditional odd carbon numbered, long-chain DCA polyesters. Biodegradation studies of 13 C-labelled polyesters in soil reveal rapid mineralization, and depolymerization by methanolysis indicates suitability for closed-loop recycling.

High-Density Polyethylene with In-Chain Photolyzable and Hydrolyzable Groups Enabling Recycling and Degradation.

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.

Biodegradable High-Density Polyethylene-like Material.

We report a novel polyester material generated from readily available biobased 1,18-octadecanedicarboxylic acid and ethylene glycol possesses a polyethylene-like solid-state structure and also tensile properties similar to high density polyethylene (HDPE). Despite its crystallinity, high melting point (Tm =96 °C) and hydrophobic nature, polyester-2,18 is subject to rapid and complete hydrolytic degradation in in vitro assays with isolated naturally occurring enzymes. Under industrial composting conditions (ISO standard 14855-1) the material is biodegraded with mineralization above 95 % within two months. Reference studies with polyester-18,18 (Tm =99 °C) reveal a strong impact of the nature of the diol repeating unit on degradation rates, possibly related to the density of ester groups in the amorphous phase. Depolymerization by methanolysis indicates suitability for closed-loop recycling.

Controlled Cobalt-Mediated Free-Radical Co- and Terpolymerization of Carbon Monoxide.

While controlled free-radical polymerizations are established for a vast range of vinyl monomers, they have not been reported for carbon monoxide, although it is a unique monomer that forms in-chain keto groups which can promote, for example, desirable photo-degradability in polyethylenes. We report organometallic-mediated radical copolymerization of carbon monoxide with ethylene initiated by an organocobaltIII compound to keto-modified polyethylenes with up to 15 mol % ketone repeat units. Terpolymerization with 2-methylene-1,3-dioxepane affords polyethylenes with in-chain ester and keto groups. Compared to ethylene homopolymerization, the controlled character of the copolymerization is strongly enhanced by the Lewis base function of carbon monoxide, which suppresses multiple unfavorable termination pathways.

Mechanistic Insights into Ni(II)-Catalyzed Nonalternating Ethylene-Carbon Monoxide Copolymerization.

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.

Molecularly Defined Polyolefin Vitrimers from Catalytic Insertion Polymerization.

Vitrimers can combine the advantageous properties of cross-linked materials with thermoplastic processability. For the prominent case of polyethylene, established post-polymerization introduction of cross-linkable moieties results in extremely heterogeneous compositions of the chains. Here, we report the generation of functionalized polyethylenes directly by catalytic insertion polymerization, with incorporated cross-linkable aryl boronic esters or alternatively acetal-protected groups suited for cross-linking with difunctional boronic esters. In addition to the desired homogeneous in-chain distribution, the reactive cross-linkable groups are enriched at the chain ends. This enables the incorporation of all chains in the network, as also supported by simulations of all chains' compositions. The uniform molecular composition of the chains reflects in resulting vitrimers' material properties, particularly lack of leaching with solvents. At the same time, cross-linking is indeed fully reversible and the vitrimers can be recycled.

Hydrophilic Catalysts with High Activity and Stability in the Aqueous Polymerization of Ethylene to High-Molecular-Weight-Polyethylene.

Water-soluble synthetic transition metal catalysts have been studied extensively for many reactions, but for olefin polymerization such catalysts have been lacking. We report herein a straightforward synthesis of phosphinephenolato NiII catalysts endowed permanently with a hydrophilic sulfonate moiety bound to the chelating ligand. These catalysts' hydrophilic active sites promote aqueous ethylene polymerization with high activity (TOF up to 6.3×104  molEthylene molNi -1 h-1 ) to high molecular weight polyethylene (HDPE), with half-lives on the order of hours also at elevated temperatures. The obtained polyethylene dispersions feature narrow particle size distributions without any aggregates.

In Vivo Olefin Metathesis in Microalgae Upgrades Lipids to Building Blocks for Polymers and Chemicals.

Sustainable sources are key to future chemicals production. Microalgae are promising resources as they fixate carbon dioxide to organic molecules by photosynthesis. Thereby they produce unsaturated fatty acids as established raw materials for the industrial production of chemical building blocks. Although these renewable feedstocks are generated inside cells, their catalytic upgrading to useful products requires in vitro transformations. A synthetic catalysis inside photoautotrophic cells has remained elusive. Here we show that a catalytic conversion of renewable substrates can be realized directly inside living microalgae. Organometallic catalysts remain active inside the cells, enabling in vivo catalytic olefin metathesis as new-to-nature transformation. Stored lipids are converted to long-chain dicarboxylates as valuable building blocks for polymers. This is a key step towards the long-term goal of producing desired renewable chemicals in microalgae as living "cellular factories".

Living Aqueous Microemulsion Polymerization of Ethylene with Robust Ni(II) Phosphinophenolato Catalysts.

Due to chain transfer events being competitive with chain growth, ethylene polymerization by P,O-chelated Ni(II) complexes usually affords low molecular weight polymers or oligomers. We now show that appropriately bulky substituted phosphinophenolato Ni(II) can polymerize in a living fashion, virtually devoid of chain transfer. Aqueous polymerizations with microemulsions of [κ2-P,O-2-(2-(2',6'-(MeO)2C6H3)C6H4)(Ph)P-6-(3',5'-(CF3)2C6H3)C6H3O-NiMe(pyridine)] (3) at 30 °C yield polyethylenes with narrow molecular weight distributions (Mw/Mn 1.02 to 1.34) and ultrahigh molecular weights (up to 2 × 106) in the form of aqueous nanoparticle dispersions. Catalyst stability and activity are maintained up to 70 °C in water.

Anhydrous Proton Transport within Phosphonic Acid Layers in Monodisperse Telechelic Polyethylenes.

Polymers bearing phosphonic acid groups have been proposed as anhydrous proton-conducting membranes at elevated operating temperatures for applications in fuel cells. However, the synthesis of phosphonated polymers and the control over the nanostructure of such polymers is challenging. Here, we report the straightforward synthesis of phosphonic acid-terminated, long-chain aliphatic materials with precisely 26 and 48 carbon atoms (C26PA2 and C48PA2). These materials combine the structuring ability of monodisperse polyethylenes with the ability of phosphonic acid groups to form strong hydrogen-bonding networks. Anhydride formation is absent so that charge carrier loss by a condensation reaction is avoided even at elevated temperatures. Below the melting temperature (Tm), both materials exhibit a crystalline polyethylene backbone and a layered morphology with planar phosphonic acid aggregates separated by 29 and 55 Å for C26PA2 and C48PA2, respectively. Above Tm, the amorphous polyethylene (PE) segments coexist with the layered aggregates. This phenomenon is especially pronounced for the C26PA2 and is identified as a thermotropic smectic liquid crystalline phase. Under these conditions, an extraordinarily high correlation length (940 Å) along the layer normal is observed, demonstrating the strength of the hydrogen bond network formed by the phosphonic acid groups. The proton conductivity in both materials in the absence of water reaches 10-4 S/cm at 150 °C. These new precise phosphonic acid-based materials illustrate the importance of controlling the chemistry to form self-assembled nanoscale aggregates that facilitate rapid proton conductivity.

Neutral Nickel(II) Catalysts: From Hyperbranched Oligomers to Nanocrystal-Based Materials.

Plastics materials are a vital component of modern technologies. They are applied, e.g., in construction, transportation, communication, water supply, or health care. Consequently, polyolefins-the most important plastics by scale-are produced in vast amounts by catalytic polymerization. Effective and selective as the catalysts used may be, their high sensitivity toward any polar compounds limits these methods to hydrocarbon reaction media and monomers like ethylene and propylene, respectively. This can be overcome by less oxophilic late transition metal catalysts, and here particularly neutral nickel(II) catalysts have seen major advances in the past few years. They stand out due to being capable of aqueous catalytic polymerizations. Aqueous polymerizations are benign processes that advantageously yield polymers in the form of particles. Moreover, these catalysts can incorporate polar monomers like acrylates, a realm previously restricted to noble metal catalysts. The introduction of polar moieties can induce properties like compatibility with metals or fibers in high performance composite materials or a desirable degradability.This Account provides a personal account of developments in the past decade. Prior findings are outlined briefly as a background. Aqueous polymerizations afford unique polyethylene morphologies as a result of the unusual underlying particle growth mechanism. Polymer single crystals are formed, which can be composed of a single ultrahigh molecular weight chain. This represents a completely disentangled state of such extremely long polymer chains, which has been long sought-after in order to overcome the difficult processing of high performance ultrahigh molecular weight materials. A key prerequisite for this approach and utilization of these catalysts, in general, is control of polymer branching and molecular weight. This is achieved via remote substituents on the Ni(II)-chelating ligand. Despite their distal position to the active site, weak secondary interactions control whether branching and chain transfer pathways compete very effectively with chain growth or are suppressed entirely. This provides access to hyperbranched oligomers, on the one hand, and enables living polymerizations to strictly linear high molecular weight polymer, on the other hand. Other advanced catalysts provide linear copolymers with in-chain polar monomer repeat units for the first time with non-noble metal active sites. Mechanistic studies further revealed that for copolymerizations with polar vinyl monomers the decisive limiting factor is irreversible termination reactions with neutral Ni(II) catalysts, rather than the well-recognized reversible blocking of coordination sites by the polar functional groups found for other types of catalysts. The mechanistic picture also implies the possibility of free-radical pathways, and their role in the formation of desirable polymer end groups and polymer blends is now being recognized. The area of neutral Ni(II) catalysts has progressed significantly in the entire range from fundamental mechanistic understanding, catalyst performance, and previously inaccessible polymer microstructures, and it is moving forward to materials through unique concepts. The unprecedented ability to incorporate functional groups into linear crystalline polyethylene also provides perspectives for much needed polyolefin materials that will not persist in the natural environment for several decades but that can be degraded by virtue of low levels of functional groups.

Neutral Unsymmetrical Coordinated Cyclophane Polymerization Catalysts.

Cyclophane structures can control steric pressure in the otherwise open spaces of square-planar d8 -metal catalysts. This elegant concept was so far limited to symmetrical coordinated metals. We report how a cyclophane motif can be generated in ligands that chelate via two different donors. An ancillary second imine in the versatile κ2 -N,O-salicylaldiminato catalyst type enables ring closure via olefin metathesis and selective double bond hydrogenation to yield a 30-membered ring efficiently. Experimental and theoretical analyses show the ancillary imine is directed away from the active site and inert for catalysis. In ethylene polymerization the cyclophane catalyst is more active and temperature stable vs. an open structure reference, notably also in polar solvents. Increased molecular weights and decreased degrees of branching can be traced to an increased energy of sterically demanding transition states by the encircling cyclophane while chain propagation remains highly efficient.

Efficient Suppression of Chain Transfer and Branching via Cs -Type Shielding in a Neutral Nickel(II) Catalyst.

An effective shielding of both apical positions of a neutral NiII active site is achieved by dibenzosuberyl groups, both attached via the same donors' N-aryl group in a Cs -type arrangement. The key aniline building block is accessible in a single step from commercially available dibenzosuberol. This shielding approach suppresses chain transfer and branch formation to such an extent that ultrahigh molecular weight polyethylenes (5×106  g mol-1 ) are accessible, with a strictly linear microstructure (<0.1 branches/1000C). Key features of this highly active (4.3×105  turnovers h-1 ) catalyst are an exceptionally facile preparation, thermal robustness (up to 90 °C polymerization temperature), ability for living polymerization and compatibility with THF as a polar reaction medium.