Sustainable Polymers: Our Evolving Understanding.

This Account discusses the evolution of our strategy to conduct environmentally responsible research in the field of polymer chemistry. To contextualize our work, we begin with a broad historical overview of the modern environmental movement, the rise of sustainability as a concept, and how chemistry has responded to these forces, which were often sharply critical of our field. We then trace our own responses, from graduate school onward, chronicling a series of experiences and research projects that molded, challenged, and reshaped how we think about sustainability in polymer science.Since beginning our independent careers in 2004, we have recognized and worked to resolve the tension between designing synthetic polymers for specific desired thermomechanical properties and minimizing environmental impact. In our early years, we were most strongly guided by the 12 Principles of Green Chemistry (12PGC), which had only recently been proposed. The authors' early research agendas had a rather narrow focus on two areas, specifically catalysis and biobased monomers, which we saw as strongly linked to sustainability. Over time, we found these areas to be too narrow in their focus, ignoring important considerations such as the capacity of monomer supply to support scale-up and the impact polymers have at the end of their usage lifetimes. With respect to monomers and catalysts, we consider descriptive metrics that quantify waste production and the toxicity of compounds used during synthesis. In terms of polymer end-of-life, we discuss hydrophobicity as a tool to help understand susceptibility to degradation in the environment as well as some of the concerns with design for degradation, a critical component of 12PGC.Now, after nearly two decades of investigation, we believe that achieving sustainability in polymer science will require us to move beyond the qualitative use of the 12PGC to a portfolio of metrics. We note a heartening increase in the availability and use of such metrics and tools across the field. These include items that provide limited insight but are relatively trivial to integrate into existing workflows such as E factor or the Toxicity Estimation Software Tool. We also appreciate the increased use of Life Cycle Assessment (LCA), which is both dramatically more thorough and difficult to deploy. Finally, we propose the creation of a national LCA center, similar to instrumental core facilities. Such a resource would enable the use of this tool across multiple phases of research and we hope would more effectively guide us to a sustainable future.

100th Anniversary of Macromolecular Science Viewpoint: Redefining Sustainable Polymers.

Although Staudinger realized makromoleküles had enormous potential, he likely did not anticipate the consequences of their universal adoption. With 6.3 billion metric tons of plastic waste now contaminating our land, water, and air, we are facing an environmental and public health crisis. Synthetic polymer chemists can help create a more sustainable future, but are we on the right path to do so? Herein, a comprehensive literature survey reveals that there has been an increased focus on "sustainable polymers" in recent years, but most papers focus on biomass-derived feedstocks. In contrast, there is less focus on polymer end-of-life fates. Moving forward, we suggest an increased emphasis on chemical recycling, which sees value in plastic waste and promotes a closed-loop plastic economy. To help keep us on the path to sustainability, the synthetic polymer community should routinely seek the systems perspective offered by life cycle assessment.

Bis{µ-4,4',6,6'-tetra-tert-butyl-2,2'-[N-(2-oxidoeth-yl)imino-dimethyl-ene]diphenolato}dialuminium(III).

The title compound, [Al(2)(C(32)H(48)NO(3))(2)], exists as a dimer with bridging ethoxide groups. It was isolated from a reaction mixture of the parent ligand and trimethyl-aluminium in tetra-hydro-furan. The geometry around the Al(III) atom is a slightly distorted trigonal-bipyramid, typical of atrane derivatives.

Mechanistic Study of Isotactic Poly(propylene oxide) Synthesis using a Tethered Bimetallic Chromium Salen Catalyst.

Initial catalyst dormancy has been mitigated for the enantioselective polymerization of propylene oxide using a tethered bimetallic chromium(III) salen complex. A detailed mechanistic study provided insight into the species responsible for this induction period and guided efforts to remove them. High-resolution electrospray ionization-mass spectrometry and density functional theory computations revealed that a µ-hydroxide and a bridged 1,2-hydroxypropanolate complex are present during the induction period. Kinetic studies and additional computation indicated that the µ-hydroxide complex is a short-lived catalyst arrest state, where hydroxide dissociation from one metal allows for epoxide enchainment to form the 1,2-hydroxypropanolate arrest state. While investigating anion dependence on the induction period, it became apparent that catalyst activation was the main contributor for dormancy. Using a 1,2-diol or water as chain transfer agents (CTAs) led to longer induction periods as a result of increased 1,2-hydroxyalkanolate complex formation. With a minor catalyst modification, rigorous drying conditions, and avoiding 1,2-diols as CTAs, the induction period was essentially removed.

{2-[Bis(3-methyl-1H-indol-2-yl)meth-yl]phenolato-κO}dimeth-yl(tetra-hydro-furan-κO)aluminium(III).

The title compound, [Al(CH(3))(2)(C(25)H(21)N(2)O)(C(4)H(8)O)], was isolated as a minor component from a reaction mixture of the parent indolyl ligand and trimethyl-aluminum in tetra-hydro-furan. The ligands adopt a distorted tetra-hedral geometry around aluminium. Obvious hydrogen-bonding interactions are not present.

Synthesis and crystal structures of some bis(3-methyl-1H-indol-2-yl)(salicyl)methanes.

Four 2,2'-bisindolylmethanes (BIMs), a useful class of polyindolyl species joined to a central carbon, were synthesized using salicylaldehyde derivatives and simple acid catalysis; these are 2-[bis(3-methyl-1H-indol-2-yl)methyl]-6-methylphenol, (IIa), 2-[bis(3-methyl-1H-indol-2-yl)methyl]-4,6-dichlorophenol, (IIb), 2-[bis(3-methyl-1H-indol-2-yl)methyl]-4-nitrophenol, (IIc), and 2-[bis(3-methyl-1H-indol-2-yl)methyl]-4,6-di-tert-butylphenol, (IId). BIMs (IIa) and (IIb) were characterized crystallographically as the dimethyl sulfoxide (DMSO) disolvates, i.e. C26H24N2O·2C2H6OS and C25H20Cl2N2O·2C2H6OS, respectively. Both form strikingly similar one-dimensional hydrogen-bonding chain motifs with the DMSO solvent molecules. BIM (IIa) packs into double layers of chains whose orientations alternate every double layer, while (IIb) forms more simply packed chains along the a axis. BIM (IIa) has a remarkably long c axis.

Carbonylation of heterocycles by homogeneous catalysts.

This article summarizes the recent developments (particularly the uses of homogeneous organometallic catalysts) in ring-opening carbonylations, ring-opening carbonylative polymerizations and ring-expansion carbonylations of heterocycles such as epoxides, aziridines, lactones and oxazolines.

A readily synthesized and highly active epoxide carbonylation catalyst based on a chromium porphyrin framework: expanding the range of available beta-lactones.

[reaction: see text] Catalytic carbonylation of epoxides to beta-lactones was effected by a highly active and selective bimetallic catalyst comprised of a chromium(III) porphyrin cation and a cobalt tetracarbonyl anion. The complex is readily synthesized from commercially available compounds in high yield. Carbonylation of numerous linear epoxides, as well as bicyclic epoxides derived from 8- and 12-membered hydrocarbons, proceeded with high activity, selectivity, and yield.

The mechanism of epoxide carbonylation by [Lewis Acid]+[Co(CO)4]- catalysts.

A detailed mechanistic investigation of epoxide carbonylation by the catalyst [(salph)Al(THF)2]+ [Co(CO)4]- (1, salph = N,N'-o-phenylenebis(3,5-di-tert-butylsalicylideneimine), THF = tetrahydrofuran) is reported. When the carbonylation of 1,2-epoxybutane (EB) to beta-valerolactone is performed in 1,2-dimethoxyethane solution, the reaction rate is independent of the epoxide concentration and the carbon monoxide pressure but first order in 1. The rate of lactone formation varies considerably in different solvents and depends primarily on the coordinating ability of the solvent. In mixtures of THF and cis/trans-2,5-dimethyltetrahydrofuran, the reaction is first order in THF. From spectroscopic and kinetic data, the catalyst resting state was assigned to be the neutral (beta-aluminoxy)acylcobalt species (salph)AlOCH(Et)CH2COCo(CO)4 (3a), which was successfully trapped with isocyanates. As the formation of 3a from EB, CO, and 1 is rapid, lactone ring closing is rate-determining. The favorable impact of donating solvents was attributed to the necessity of stabilizing the aluminum cation formed upon generation of the lactone.

Catalytic carbonylation of beta-lactones to succinic anhydrides.

A well-defined, highly active and selective catalyst for the synthesis of succinic anhydrides from CO and beta-lactones is reported. At 200 psi of CO, the catalyst [(N,N'-bis(3,5-di-tert-butylsalicylidene)phenylenediamino)Al(THF)2][Co(CO)4] carbonylates beta-propiolactones to succinic anhydrides in high yield. (R)-beta-Butyrolactone is carbonylated to (S)-methylsuccinic anhydride with clean inversion of stereochemistry, while cis-2,3-dimethyl-beta-propiolactone yields exclusively trans-2,3-dimethylsuccinic anhydride. These data are consistent with a mechanism involving nucleophilic attack by [Co(CO)4]- on the beta carbon of the lactone, followed by CO insertion and anhydride formation.

Synthesis of beta-lactones: a highly active and selective catalyst for epoxide carbonylation.

A new highly active and selective catalyst for the synthesis of beta-lactones from CO and epoxides is reported. The catalyst, [(N,N'-bis(3,5-di-tert-butylsalicylidene) phenylenediamino)Al(THF)2][Co(CO)4] ([(salph)Al(THF)2][Co(CO)4]) is easily prepared from the corresponding (salph)AlCl and NaCo(CO)4. At 50 degrees C and 880 psi of CO, the catalyst (1 mol %) carbonylates epoxides such as propylene oxide, 1-butene oxide, epichlorohydrin, and isobutylene oxide to the lactones beta-butyrolactone, beta-valerolactone, gamma-chloro-beta-butyrolactone, and beta-methyl-beta-butyrolactone in high yield. (R)-Propylene oxide was carbonylated to (R)-beta-butyrolactone with retention of stereochemistry.