Synthesis of High-Molecular-Weight Poly(ether-alt-ester) by Selective Double Ring-Opening Polymerization of Spiroorthoesters.

We report the selective double ring-opening polymerization of presequenced spiroorthoester monomers to form high-molecular-weight (≈90 kDa) poly(ether-alt-ester)s with a simple cationic alkyl gallium catalyst. The selective formation of double ring-opened polymer units was confirmed by NMR and IR spectroscopies. Thermal and rheological properties of homo- and copolymers were further characterized by differential scanning calorimetry, thermogravimetric analysis, and stress-controlled rotational rheometry. Linear viscoelastic moduli show that these systems are well entangled (plateau modulus), thereby possessing nearly terminal relaxation at long time scales (low frequencies) and Rouse segmental dynamics at short time scales (high frequencies) with characteristic slopes. These are the highest-molecular-weight poly(ether-alt-ester)s reported to date.

Impact of counterion valency on the rheology of sulfonated cellulose nanocrystal hydrogels.

A systematic rheological study on the influence of valency of different counterions on the properties of CNC hydrogels was carried out. Rheo-polarized microscopy was used to prove that preshear of 500 s-1 for 1 min is adequate to completely breakdown agglomerates in the suspension. Furthermore, a rest period of 30 min is sufficient to recover the equilibrium structure of hydrogels. Changing counterions from monovalent (Na+, K+, Li+), to divalent (Mg2+, Ca2+) and to trivalent (Al3+) influenced the network formation. CNC suspensions with monovalent counterions are isotropic at 3 wt%, anisotropic with chiral nematic structures at 5 wt% and form birefringent gels at 7 wt%. Conversely, divalent and trivalent counterions facilitate network formation, leading to gel like behavior at all concentrations. Sonication of CNC samples with monovalent counterions lowers the viscosity by two orders of magnitude while the opposite is true for multivalent counterions due to the formation of strong networks. The varying rheological properties displayed from CNCs with different counter ions may influence the use of CNC as rheological modifiers in fluid-based applications.

Cooperative Initiation in a Dinuclear Indium Complex for CO2 Epoxide Copolymerization.

Dinuclear indium complexes have been synthesized and characterized. These include neutral and cationic indium complexes supported by a Schiff base ligand bearing a binaphthol linker. The new compounds were investigated for alternating copolymerization of CO2 and cyclohexene oxide. In particular, the neutral indium chloride complex (±)-[(ONapNiN)InCl2]2 (4) showed high conversion of cyclohexene oxide and selectivity for poly(cyclohexene carbonate) formation without cocatalysts at 80 °C under various CO2 pressures (2-30 bar). Importantly, the reactivity of the dinuclear indium chloride complex 4 is drastically different from that of the mononuclear indium chloride complex (±)-(NNiOtBu)InCl2 (5), suggesting a cooperative initiation mechanism involving the two indium centers in 4.

Thermally stable zinc hydride catalyst for hydrosilylation of CO2 to silyl formate at atmospheric pressure.

Neutral zinc complexes supported by H[PNNO], a diaminophenolate ligand bearing a pendant phosphine group, were synthesized and characterized. The phosphine arm adopts two different configurations in solution and prevents aggregation. The monomeric zinc hydride complex is stable at elevated temperatures up to 125 °C and reacts readily with CO2 to afford a zinc formate complex. The zinc hydride is active for CO2 hydrosilylation at atmospheric CO2 pressure and is selective for CO2 reduction to the silyl-formate product.

Temperature triggered alternating copolymerization of epoxides and lactones via pre-sequenced spiroorthoester intermediates.

We report the alternating copolymerization of caprolactone and epoxide through the in situ formation of pre-sequenced spiroorthoester monomer. The reaction is catalyzed by the temperature triggered, bifunctional cationic indium complex (±)-[(NNiOtBu)In(CH2SiMe3)][B(C6F5)4] (1). 1 can catalyze the coupling of epoxide and lactone to form spiroorthoester at 60 °C and its double ring-opening polymerization at 110 °C to form poly(ether-alt-ester). The post-polymerization modification and degradation of the poly(ether-alt-ester) are further investigated.

Comparison of Imine- and Phosphinimine-Supported Indium Complexes: Tuning the Reactivity for the Sequential and Simultaneous Copolymerization of Lactide and ε-Caprolactone.

Imine- and phosphinimine-supported indium complexes were used as catalysts in the polymerization of racemic lactide and ε-caprolactone as well as their copolymerization by the sequential and simultaneous addition of monomers. Tuning the electronics and sterics of the indium centers by either (i) changing the nature of the nitrogen donors and (ii) coordinating a hemilabile side group had a significant effect on the reactivity of the complexes, their stability, and their control in the synthesis of block copolymers. Specifically, the imine-supported complex (5) showed the highest activity in the homo- and copolymerization of the cyclic esters, in contrast to the phosphinimine-supported complex (7), which was significantly slower and less stable. The presence of morpholine and thiomorpholine hemilabile side groups either reduced the activity or prevented the formation of alkoxide complexes.

Indium-Catalyzed CO2/Epoxide Copolymerization: Enhancing Reactivity with a Hemilabile Phosphine Donor.

Group 13 metal complexes have emerged as powerful catalysts for transforming CO2 into added-value products. However, direct comparisons of reactivity between Al, Ga, and In catalysts are rare. We report aluminum (1), gallium (2), and indium (3) complexes supported by a half-salen H[PNNO] ligand with a pendent phosphine donor and investigate their activity as catalysts for the copolymerization of CO2 and cyclohexene oxide. In solution, the P-donor is dissociated for the Al and Ga complexes while for the In complex it exhibits hemilabile behavior. The indium complex shows higher conversion and selectivity than the Al or Ga analogues. The mechanism of the reaction was studied by NMR and FTIR spectroscopy experiments as well as structural characterization of off-cycle catalytic intermediate indium trichloride complex [(PNNO)InCl3][TBA] (4). This study highlights the impact of a hemilabile phosphine group on group 13 metals and provides a detailed analysis of the initiation step in CO2/epoxide copolymerization reactions.

Toward Biodegradable Electronics: Ionic Diodes Based on a Cellulose Nanocrystal-Agarose Hydrogel.

Bioderived cellulose nanocrystals (CNCs) are used to create light, flexible, biocompatible, and biodegradable electronic devices. Herein, surface modification of cellulose nanocrystals was employed to fabricate cationic and anionic CNCs. Subsequently, we demonstrated rectification behavior from a fixed junction between two agarose hydrogels doped with cationic and anionic cellulose nanocrystals. The current rectification ratio reaches 70 reproducibly, which is significantly higher than that for analogous diodes generated with microfibrillated cellulose (∼15) and the first polyelectrolyte gel diode (∼40). The current-voltage characteristics of the CNC-hydrogel diode are influenced by concentration, gel thickness, scanning frequency, and applied voltage. The high surface area of CNC resulted in high charge density after surface modification, which in turn resulted in good rectification behavior from only small amounts of dopant material.

Dinucleating Amino-Phenolate Platform for Zinc Catalysts: Impact on Lactide Polymerization.

We report imine- and amine-based dinucleating ligands bearing a bisphenol backbone and explore their coordination chemistry with zinc to form zinc alkyl, alkoxide, acetate, and amide complexes. Full characterization of the complexes shows that this ligand framework can support dinuclear and trinuclear complexes. We explore the reactivity of the zinc alkyl and alkoxide complexes as catalysts for the ring opening polymerization of lactide and compared this reactivity to analogous mononuclear complexes. We show that 1) The amine-based complexes are more reactive than the imine-based analogues; 2) The trinuclear zinc alkyl species show unusual control and reproducibility for lactide polymerization; and 3) The extent of bimetallic cooperation is hampered by the ability of the ligand framework to form trinuclear clusters.

Cationic indium catalysts for ring opening polymerization: tuning reactivity with hemilabile ligands.

This is a comprehensive study of the effects of rationally designed hemilabile ligands on the stability, reactivity, and change in catalytic behavior of indium complexes. We report cationic alkyl indium complexes supported by a family of hemi-salen type ligands bearing hemilabile thiophenyl (2a), furfuryl (2b) and pyridyl (2c) pendant donor arms. Shelf-life and stability of these complexes followed the trend 2a < 2b < 2c, showing direct correlation to the affinity of the pendant donor group to the indium center. Reactivity towards polymerization of epichlorohydrin and cyclohexene oxide followed the trend 2a > 2b > 2c with control of polymerization following an inverse relationship to reactivity. Surprisingly, 2c polymerized racemic lactide without an external initiator, likely through an alkyl-initiated coordination-insertion mechanism.

Cationic indium complexes for the copolymerization of functionalized epoxides with cyclic ethers and lactide.

We report the first example of discrete cationic indium complexes for the copolymerization of epoxides, cyclic ethers, and lactide. [SalenIn][SbF6] in particular proved to be a highly active catalyst for the homo-polymerization of functionalized epoxides and their copolymerization with other cyclic ethers THF, oxetane and oxepane. This catalyst also proved competent in the polymerization of epichlorohydrin and lactide, forming copolymers with good activity and control. Investigation of the role of counteranions and solvent donors on the kinetics of polymerization of epoxides revealed a subtle effect of solvents on initiation rates.

Indium Catalysts for Ring Opening Polymerization: Exploring the Importance of Catalyst Aggregation.

Inexorably, the environmental persistence and damage caused by polyolefins have become major drawbacks to their continued long-term use. Global shifts in thinking from fossil-fuel to renewable biobased resources have urged researchers to focus their attention on substituting fossil-fuel based polymers with renewable and biodegradable alternatives on an industrial scale. The recent development of biodegradable polyesters from ring opening polymerization (ROP) of bioderived cyclic ester monomers has emerged as a promising new avenue toward this goal. Ever increasing numbers of metal-based initiators have been reported in the literature for the controlled ROP of cyclic esters, in particular for the polymerization of lactide to produce poly(lactic acid) (PLA). PLA has several material weaknesses, which hinder its use as a replacement for commodity plastics. Despite many advances in developing highly active and controlled catalysts for lactide polymerization, no single catalyst system has emerged to replace industrially used catalysts and provide access to PLA materials with improved properties. We reported the first example of indium(III) for the ring opening polymerization of lactide. Since then, indium(III) has emerged as a useful Lewis acid in initiators for the controlled polymerization of lactide and other cyclic esters. In particular, we have developed a large family of chiral dinuclear indium complexes bearing tridentate diaminophenolate ligands and tetradentate salen and salan ligands. Complexes within our tridentate ligand family are highly active initiators for the moderately isoselective living and immortal polymerization of rac-lactide, as well as other cyclic esters. We have shown that subtle steric effects influence aggregation in these systems, with polymerization typically proceeding through a dinuclear propagating species. In addition, profound effects on polymerization activities have been observed for central tertiary versus secondary amine donors in these and other related systems. In contrast, our well-controlled and highly active chiral indium salen systems are more isoselective than the tridentate analogues and polymerize lactide via a mononuclear propagating species. Again, we have noticed that subtle steric and electronic changes to the ligand can influence both polymerization activity and stereoselectivity via aggregation phenomena. Recently, we have reported a promising new chiral indium catalyst supported by a tetradentate salan ligand. This catalyst is remarkably water and air stable and can be activated by linear and branched alcohols to provide controlled access to multiblock copolymers in air. This catalyst represents an important step forward toward generating new, commercially relevant catalysts for ROP of cyclic esters to produce novel biodegradable polymers, and highlights the unique value of indium-based catalysts in the field.

A Comparison of Gallium and Indium Alkoxide Complexes as Catalysts for Ring-Opening Polymerization of Lactide.

The impact of the metal size and Lewis acidity on the polymerization activity of group 13 metal complexes was studied, and it was shown that, within the same ligand family, indium complexes are far more reactive and selective than their gallium analogues. To this end, gallium and aluminum complexes supported by a tridentate diaminophenolate ligand, as well as gallium complexes supported by N,N'-ethylenebis(salicylimine)(salen) ligands, were synthesized and compared to their indium analogues. Using the tridentate ligand set, it was possible to isolate the gallium chloride complexes 3 and (±)-4 and the aluminum analogues 5 and (±)-6. The alkoxygallium complex (±)-2, supported by a salen ligand, was also prepared and characterized and, along with the three-component system GaCl3/BnOH/NEt3, was tested for the ring-opening polymerization of lactide and ε-caprolactone. The polymerization rates and selectivities of both systems were significantly lower than those for the indium analogues. The reaction of (±)-2 with 1 equiv of lactide forms the first insertion product, which is stable in solution and can be characterized at room temperature. In order to understand the differences of the reactivity within the group 13 metal complexes, a Lewis acidity study using triethylphosphine oxide (the Gutmann-Beckett method) was undertaken for a series of aluminum, gallium, and indium halide complexes; this study shows that indium halide complexes are less Lewis acidic than their aluminum and gallium analogues. Density functional theory calculations show that the Mulliken charges for the indium complexes are higher than those for the gallium analogues. These data suggest that the impact of ligands on the reactivity is more significant than that of the metal Lewis acidity.

The Role of Nitrogen Donors in Zinc Catalysts for Lactide Ring-Opening Polymerization.

The electronic effects of nitrogen donors in zinc catalysts for ring-opening polymerization of cyclic esters were investigated. Alkyl and benzyloxy zinc complexes supported by tridentate diamino- and aminoimino phenolate ligands were synthesized, and their solid-state and solution structures characterized. The solution-state structures showed that the alkyl complexes are mononuclear, while the alkoxy complexes are dimeric with the ligands coordinated with different denticities depending on the nature of the ligand donors. The catalytic activities of these compounds toward the ring-opening polymerization of racemic lactide were studied and showed that catalysts with secondary and imine nitrogen donors are more active than analogues with tertiary amines.

Dinucleating Ligand Platforms Supporting Indium and Zinc Catalysts for Cyclic Ester Polymerization.

The synthesis of the first alkoxide-bridged indium complex supported by a chiral dinucleating ligand platform (1), along with its zinc analogue (2), is reported. Both complexes are synthesized in a one-pot reaction starting from a chiral dinucleating bis(diamino)phenolate ligand platform, sodium ethoxide, and respective metal salts. The dinucleating indium analogue (7) based on an achiral ligand backbone is also reported. Indium complexes bearing either the chiral or achiral ligand catalyze the ring-opening polymerization of racemic lactide (rac-LA) to afford highly heterotactic poly(lactic acid) (PLA; Pr > 0.85). The indium complex bearing an achiral ligand affords essentially atactic PLA from meso-LA. The role of the dinucleating ligand structure in catalyst synthesis and polymerization activity is discussed.

Probing the role of secondary versus tertiary amine donor ligands for indium catalysts in lactide polymerization.

The role of the central amine donor in a previously reported dinuclear indium catalyst, [N(Me2)N(H)O)InCl]2(µ-Cl)(µ-OEt) (1), for the polymerization of lactide was investigated through experimental methods. The solid state structural data of a series of dimeric complexes related to 1, including the previously reported bromide derivative [(N(Me2)N(H)O)InBr](µ-Br)(µ-OEt) (2) and the newly synthesized methylated derivative [(N(Me2)N(Me)O)InCl]2(µ-Cl)(µ-OEt) (6), showed that weak hydrogen bonding may be present within some of these complexes in the solid state. The polymerization of rac-lactide with 2, 6, and a related achiral complex [(L(H))InCl]2(µ-Cl)(µ-OEt) (8) synthesized for this study indicates that hydrogen bonding may not influence the reactivity of these compounds. The nature of the central amine donor may play a role in tuning the reactivity of these types of catalysts. Catalysts with central secondary amine donors, such as complexes 1, 2, and 8, are 2 orders of magnitude more reactive than those with central tertiary amine donors, such as complex 6.

Redox control of group 4 metal ring-opening polymerization activity toward L-lactide and ε-caprolactone.

The activity of several group 4 metal alkoxide complexes supported by ferrocene-based ligands was controlled using redox reagents during the ring-opening polymerization of l-lactide and ε-caprolactone. Switching in situ between the oxidized and reduced forms of a metal complex resulted in a change in the corresponding rate of polymerization. Opposite behavior was observed for each monomer used. One-pot copolymerization of the two monomers to give block copolymers was also achieved.

Role of aggregation in the synthesis and polymerization activity of SalBinap indium alkoxide complexes.

The reaction of racemic SalBinap ligand, (±)-H2(ONN*OMe), with InCl3 and excess NaOEt generated a mixture of two dinuclear compounds [(µ-κ(2)-ONN*OMe)In(µ-OEt)]2 (1a) and [κ(4)-ONN*OMe)In(µ-OEt)]2 (1b), which were isolated and fully characterized. Polymerization of racemic lactide with 1a and 1b was slow in refluxing THF and showed only modest stereoselectivity. Catalyst 1b displayed better control than 1a, with the experimental molecular weights of the resulting poly(lactic acid) in agreement with the expected values. The higher-than-expected molecular weights observed in polymers formed by 1a were due to partial initiation of the catalyst. The reaction of (±)-H2(ONN*OtBu) with InCl3 yielded (κ(4)-ONN*OtBu)InCl (2); however, further reactivity of the compound formed a mixture of products. An attempt to prevent aggregation by reacting (±)-H2(ONN*OMe) with InCl3 and excess NaO(i)Pr yielded an intractable mixture, including [(µ-κ(2)-ONN*OMe)In]2(µ-Cl)(µ-OH) (3). The thermal stabilities of compounds 1a and 1b under polymerization conditions were investigated. Examination of the polymerization behavior of complexes 1a and 1b and the reaction equilibrium between the two illustrates the importance of aggregation in indium salen complexes compared to their aluminum counterparts.

A highly active and site selective indium catalyst for lactide polymerization.

Chiral indium salen complexes are highly active, isoselective catalysts for the ring opening polymerization of racemic lactide. The polymerizations are well controlled and polymers with high molecular weights and low molecular weight distributions are obtained. Preliminary kinetic investigations with the enantiopure complex confirm enantiomorphic site control as the dominant contributor to selectivity and formation of block copolymers.

Mechanism of living lactide polymerization by dinuclear indium catalysts and its impact on isoselectivity.

A family of racemic and enantiopure indium complexes 1-11 bearing bulky chiral diaminoaryloxy ligands, H(NNO(R)), were synthesized and fully characterized. Investigation of both the mono- and the bis-alkoxy-bridged complexes [(NNO(R))InX](2)[µ-Y][µ-OEt] (5, R = (t)Bu, X = Y = Cl; 8, R = Me, X = I, Y = OEt) by variable temperature, 2D NOESY, and PGSE NMR spectroscopy confirmed dinuclear structures in solution analogous to those obtained by single-crystal X-ray crystallography. The dinuclear complexes in the family were highly active catalysts for the ring-opening polymerization (ROP) of lactide (LA) to form poly(lactic acid) (PLA) at room temperature. In particular, complex 5 showed living polymerization behavior over a large molecular weight range. A detailed investigation of catalyst stereoselectivity showed that, although (R,R/R,R)-5 is highly selective for l-LA, only atactic PLA is obtained in the polymerization of racemic LA. No such selectivity was observed for complex 8. Importantly, the selectivities obtained for the ROP of racemic LA with (R,R/R,R)-5 and (R,R/R,R)-8 are different and, along with kinetics investigations, suggest a dinuclear propagating species for these complexes.