Unraveling the Mechanism of Catalyzed Melt-Phase Polyester Depolymerization via Studies of Kinetics and Model Reactions.

Developing a mechanistic understanding of catalyzed melt-phase depolymerization processes is of utmost importance to the rapidly expanding field of circular polymers with a closed chemical loop. Herein, we present a methodology to probe the mechanism of metal-catalyzed melt-phase depolymerization of polyesters utilizing an approach centered on studies of kinetics by thermogravimetric analysis and model reactions. Kinetic parameters associated with the prototypical Lewis-acid-catalyzed depolymerization of representative polyesters, including poly(δ-valerolactone) (PVL), poly(lactic acid), and poly(γ-butyrolactone), are elucidated. Focusing on PVL for further investigation of the depolymerization mechanism, effects of its molar mass, topology, and end-group chemistry are examined in detail. Overall, a catalyzed ring-closing depolymerization process to monomer from the polyester hydroxyl-chain ends is proposed as the key mechanistic step, although the process has a relatively large zip length (≈ 320) and follows nonimmortal depolymerization kinetics.

Chain-End Controlled Depolymerization Selectivity in α,α-Disubstituted Propionate PHAs with Dual Closed-Loop Recycling and Record-High Melting Temperature.

Within the large poly(3-hydroxyalkanoate) (PHA) family, C3 propionates are much less studied than C4 butyrates, with the exception of α,α-disubstituted propionate PHAs, particularly poly(3-hydroxy-2,2-dimethylpropionate), P3H(Me)2P, due to its high melting temperature (Tm ∼ 230 °C) and crystallinity (∼76%). However, inefficient synthetic routes to its monomer 2,2-dimethylpropiolactone [(Me)2PL] and extreme brittleness of P3H(Me)2P largely hinder its broad applications. Here, we introduce simple, efficient step-growth polycondensation (SGP) of a hydroxyacid or methyl ester to afford P3H(Me)2P with low to medium molar mass, which is then utilized to produce lactones through base-catalyzed depolymerization. The ring-opening polymerization (ROP) of the 4-membered lactone leads to high-molar-mass P3H(Me)2P, which can be depolymerized by hydrolysis to the hydroxyacid in 99% yield or methanolysis to the hydroxyester in 91% yield, achieving closed-loop recycling via both SGP and ROP routes. Intriguingly, the chain end of the SGP-P3H(Me)2P determines the depolymerization selectivity toward 4- or 12-membered lactone formation, while both can be repolymerized back to P3H(Me)2P. Through the formation of copolymers P3H(Me/R)2P (R = Et, nPr), PHAs with high tensile strength and ductility, coupled with high barriers to water vapor and oxygen, have been created. Notably, the PHA structure-property study led to P3H(nPr)2P with a record-high Tm of 266 °C within the PHA family.

Dual Recycling of Depolymerization Catalyst and Biodegradable Polyester that Markedly Outperforms Polyolefins.

Chemically recyclable, circular polymers continue to attract increasing attention, but rendering both catalysts for depolymerization and high-performance polymers recyclable is a more sustainable yet challenging goal. Here we introduce a dual catalyst/polymer recycling system in that recyclable inorganic phosphomolybdic acid catalyzes selective depolymerization of high-ceiling-temperature biodegradable poly(δ-valerolactone) in bulk phase, which, upon reaching suitable molecular weight, exhibits outstanding mechanical performance with a high tensile strength of ≈66.6 MPa, fracture strain of ≈904 %, and toughness of ≈308 MJ m-3 , and thus markedly outperforms commodity polyolefins, recovering its monomer in pure state and quantitative yield at only 100 °C. In sharp contrast, the uncatalyzed depolymerization not only requires a high temperature of >310 °C but is also low yielding and non-selective. Importantly, the recovered monomer can be repolymerized as is to reproduce the same polymer, thereby closing the circular loop, and the recycled catalyst can be reused repeatedly for depolymerization runs without loss of its catalytic activity and efficiency.

Chemoselective, Stereospecific, and Living Polymerization of Polar Divinyl Monomers by Chiral Zirconocenium Catalysts.

This contribution reports the first chemoselective, stereospecific, and living polymerization of polar divinyl monomers, enabled by chiral ansa-zirconocenium catalysts through an enantiomorphic-site controlled coordination-addition polymerization mechanism. Silyl-bridged-ansa-zirconocenium ester enolate 2 has been synthesized and structurally characterized, but it exhibits low to negligible activity and stereospecificity in the polymerization of polar divinyl monomers including vinyl methacrylate (VMA), allyl methacrylate (AMA), 4-vinylbenzyl methacrylate (VBMA), and N,N-diallyl acrylamide (DAA). In contrast, ethylene-bridged-ansa-zirconocenium ester enolate 1 is highly active and stereospecific in the polymerization of such monomers including AMA, VBMA, and DAA. The polymerization by 1 is perfectly chemoselective for all four polar divinyl monomers, proceeding exclusively through conjugate addition across the methacrylic C═C bond, while leaving the pendant C═C bonds intact. The polymerization of DAA is most stereospecific and controlled, producing essentially stereoperfect isotactic PDAA with [mmmm] > 99%, M(n) matching the theoretical value (thus a quantitative initiation efficiency), and a narrow molecular weight distribution (D = 1.06-1.16). The stereospecificity is slightly lower for the AMA polymerization but still leading to highly isotactic poly(allyl methacrylate) (PAMA) with 95-97% [mm]. The polymerization of VBMA is further less stereospecific, affording PVBMA with 90-94% [mm], while the polymerization VMA is least stereospecific. Several lines of evidence from both homo- and block copolymerization results have demonstrated living characteristics of the AMA polymerization by 1. Mechanistic studies of this polymerization have yielded a monometallic coordination-addition polymerization mechanism involving the eight-membered chelating intermediate. Post-functionalization of isotactic polymers bearing the pendant vinyl group on every repeating unit via the thiol-ene "click" reaction achieves a full conversion of all the pendant double bonds to the corresponding thioether bonds. Photocuring of such isotactic polymers is also successful, producing an elastic material readily characterizable by dynamic mechanical analysis.

Chemically circular, mechanically tough, and melt-processable polyhydroxyalkanoates.

Polyhydroxyalkanoates (PHAs) have attracted increasing interest as sustainable plastics because of their biorenewability and biodegradability in the ambient environment. However, current semicrystalline PHAs face three long-standing challenges to broad commercial implementation and application: lack of melt processability, mechanical brittleness, and unrealized recyclability, the last of which is essential for achieving a circular plastics economy. Here we report a synthetic PHA platform that addresses the origin of thermal instability by eliminating α-hydrogens in the PHA repeat units and thus precluding facile cis-elimination during thermal degradation. This simple α,α-disubstitution in PHAs enhances the thermal stability so substantially that the PHAs become melt-processable. Synergistically, this structural modification also endows the PHAs with the mechanical toughness, intrinsic crystallinity, and closed-loop chemical recyclability.

1,1'-Binaphthyl-2,2'-diyl benzyl-phos-phoramidate.

In the title compound, C(27)H(20)NO(3)P, the P atom exhibits a somewhat distorted PNO(3) tetra-hedral geometry, with the O-P-O angle for the binaphthyl fragment being 102.82 (6)°. The dihedral angle between the naphthyl ring systems is 59.00 (2)°. In the crystal, inversion dimers linked by pairs of N-H⋯O hydrogen bonds generate R(2) (2)(8) loops.

Triethyl-ammonium 1,1'-binaphthyl-2,2'-diyl phosphate.

In the crystal structure of the title compound, C(6)H(16)N(+)·C(20)H(12)O(4)P(-), an N-H⋯O inter-action links the cation to the anion. The N atom in the triethyl-ammonium cation exhibits a trigonal-bipyramidal coordination geometry and forms an N-H⋯O inter-action with one phosphate O atom of the 1,1'-binaphthyl-2,2'-diyl phosphate ligand. A bifurcated C-H⋯O inter-action with the other phosphate O atom links molecules along the a axis. The dihedral angle between the two naphthyl ring systems is 58.92 (3)°. The refined Flack parameter value of 0.50 (10) indicates inversion twinning.

p-Tolyl-methanaminium cyclo-hexane-1,2-diyl phosphate.

In the title mol-ecular salt, C(8)H(12)N(+)·C(6)H(10)O(4)P(-), the cation and anion are connected by N-H⋯O hydrogen bonds. The C atoms of the cyclo-hexane ring are disordered over two sets of sites in a 0.51 (4):0.49 (4) occupancy ratio to generate two superimposed chair conformations. One of the terminal phosphate O atoms is also disordered in a 0.62 (2):0.38 (2) ratio.

Regioselective Hydrogenation of Itaconic Acid to γ-Isovalerolactone by Transition-Metal Nanoparticle Catalysts.

Current methods for hydrogenation of bio-derived itaconic acid (IA) lead to a mixture of isomeric lactone products. Transition-metal nanoparticles (TM-NPs), in situ-generated through thermolysis of TM(0) (Ru, Fe, W, Cr) carbonyls, in particular Ru-NPs, were found to catalyze regioselective hydrogenation of IA by syngas (2 H2 /CO) into γ-isovalerolactone (GiVL) in approximately 70 % isolated yield. Key sustainability features of this new route include: a one-pot direct transformation of bio-renewable IA into value-added GiVL selectively, use of inexpensive and renewable syngas in aqueous solution, and development of a supported recyclable NP catalyst system, Al2 O3 -Ru-NPs.

Chemoselective Lewis pair polymerization of renewable multivinyl-functionalized γ-butyrolactones.

Multivinyl-functionalized γ-butyrolactones, γ-vinyl-γ-methyl-α-methylene-γ-butyrolactone (γVMMBL) and γ-allyl-γ-methyl-α-methylene-γ-butyrolactone (γAMMBL), have been synthesized from biorenewable ethyl levulinate and effectively polymerized by Lewis pairs consisting of an organic N-heterocyclic carbene Lewis base and a strong organo-Lewis acid E(C6F5)3 (E = Al, B). This Lewis pair polymerization is quantitatively chemoselective, proceeds exclusively via polyaddition across the conjugated α-methylene double bond without participation of the γ-vinyl or γ-allyl double bond, and produces high-molecular-weight functionalized polymers with unimodal molecular-weight distributions. The Al-based Lewis pair produces a polymer with approximately 5.5 times higher molecular weight than that produced by the B-based Lewis pair. The resulting vinyl-functionalized polymers are soluble in common organic solvents and stable at room temperature, and can be thermally cured into crosslinked materials.This article is part of the themed issue 'Frustrated Lewis pair chemistry'.

Recyclable Earth-Abundant Metal Nanoparticle Catalysts for Selective Transfer Hydrogenation of Levulinic Acid to Produce γ-Valerolactone.

Nanoparticles (NPs) derived from earth-abundant metal(0) carbonyls catalyze conversion of bio-derived levulinic acid into γ-valerolactone in up to 93% isolated yield. This sustainable and green route uses non-precious metal catalysts and can be performed in aqueous or ethanol solution without using hydrogen gas as the hydrogen source. Generation of metal NPs using microwave irradiation greatly enhances the rate of the conversion, enables the use of ethanol as both solvent and hydrogen source without forming the undesired ethyl levulinate, and affords recyclable polymer-stabilized NPs.

Organocatalytic and Chemoselective Polymerization of Multivinyl-Functionalized γ-Butyrolactones.

Achieving complete chemoselectivity in the polymerization of multivinyl polar monomers is an important yet challenging task, currently achievable only by metal- or metalloid-mediated polymerization processes but in a noncatalytic fashion. Now this work shows that organic N-heterocyclic carbene (NHC) catalysts effect rapid, chemoselective, and catalytic polymerization of multivinyl-functionalized γ-butyrolactones, particularly γ-vinyl-α-methylene-γ-butyrolactone (VMBL). Thus, the NHC-catalyzed polymerization of VMBL not only is quantitatively chemoselective, proceeding exclusively via polyaddition across the conjugated α-methylene double bond while leaving the γ-vinyl double bond intact, but also requires only an exceptionally low catalyst loading of 50 ppm, thus, exhibiting a remarkably high catalyst turnover frequency of 80000 h-1 and producing on average 33.6 polymer chains of Mn = 73.8 kg/mol per NHC molecule. The resulting PVMBL can be either thermally cured into cross-linked materials or postfunctionalized with the thiol-ene "click" reaction to achieve complete conversion of the pendant vinyl group on every repeat unit into the corresponding thioether.

Gallium and indium complexes containing the bis(imino)phenoxide ligand: synthesis, structural characterization and polymerization studies.

A series of gallium and indium complexes containing a bis(imino)phenolate ligand framework were synthesized and completely characterized with different spectroscopic techniques. The molecular structures of a few complexes were determined using single crystal X-ray diffraction studies. These compounds were found to be extremely active towards the bulk ring opening polymerization (ROP) of lactides yielding polymers with high number average molecular weight (Mn) and controlled molecular weight distributions (MWDs). The neutral complexes produce isotactic enriched poly(lactic acid) (PLA) from rac-lactide (rac-LA) under melt conditions, whereas the ionic complex produces atactic PLA. The polymerizations are controlled, as evidenced by the narrow molecular distribution (MWDs) of the isolated polymers in addition to the linear nature of number average molecular weight (Mn) versus conversion plots with variations in monomer to catalyst ratios. The kinetic and mechanistic studies associated with these polymerizations have been performed.

Chiral and achiral (imino)phenoxy-based cationic group 4 non-metallocene complexes as catalysts for polymerization of renewable α-methylene-γ-butyrolactones.

Protonolysis of M(Bn)4 (M = Zr, Ti; Bn = benzyl) with equimolar 2,4-di-tert-butyl-6-[(2,6-diisopropylphenylimino)methyl]phenol [(2,6-(i)Pr2C6H3)N=C(3,5-(t)Bu2C6H2)OH] in toluene at -30 °C to 25 °C cleanly affords the corresponding achiral (imino)phenoxy-tribenzyl complexes, [(2,6-(i)Pr2C6H3)N=C(3,5-(t)Bu2C6H2)O]Zr(Bn)3 (1) and [(2,6-(i)Pr2C6H3)N=C(3,5-(t)Bu2C6H2)O]Ti(Bn)3 (2). A chiral dibenzyl complex 3 incorporating the unsymmetric, tetradentate amino(imino)bis(phenoxy) ligand, [2,4-Br2C6H2(O)(6-CH2(NC5H9))CH2N=CH(2-adamantyl-4-MeC6H2O)]Zr(Bn)2 (3), has also been prepared using the same protonolysis protocol. Abstractive activation of 1 with B(C6F5)3·THF in CD2Cl2 at room temperature (RT) affords clean, quantitative formation of the corresponding zirconium cation [((2,6-(i)Pr2C6H3)N=C(3,5-(t)Bu2C6H2)O)Zr(Bn)2(THF)](+)[BnB(C6F5)3](-) (4). Likewise, benzyl abstraction of 2 with B(C6F5)3·THF in CD2Cl2 at RT generates the cationic titanium complex [((2,6-(i)Pr2C6H3)N=C(3,5-(t)Bu2C6H2)O)Ti(Bn)2(THF)](+)[BnB(C6F5)3](-) (5), accompanied by a small amount of decomposed species as a result of C6F5 transfer. The dibenzyl cations 4 and 5 have been characterized spectroscopically, and their structures have been confirmed by single crystal X-ray diffraction analysis. Characteristics of the coordination polymerization of renewable α-methylene-γ-butyrolactone monomers by the cationic catalysts derived from achiral complexes 1 and 2 as well as chiral complex 3 have been investigated, representing the first study of such polymerization by non-metallocene catalysts.

Bis(imino)phenoxide complexes of zirconium: synthesis, structural characterization and solvent-free ring-opening polymerization of cyclic esters and lactides.

Bis(imino)phenoxide complexes of zirconium possess spectacular reactivity towards the solvent-free polymerization of cyclic ester monomers and lactides. Polymerization of lactide is living and the resulting product has exceptionally high number average molecular weights (Mn). Polymerization of ß-butyrolactone gives syndiotactic poly(3-hydroxybutyrate) with good Mn and molecular weight distribution (MWD).