Catalytic Ring-opening Polymerization Research Articles

Ligand‐directed assembly of multimetallic aluminum complexes: Synthesis, Structure and ROP catalysis

Multinuclear aluminum complexes are useful catalysts for the ring opening polymerization (ROP) of ε‐caprolactone (ε‐CL), often outperforming monometallic analogues in the production of biodegradable polycaprolactone (PCL). These complexes require control over metal‐metal distance, ligand structure, and substituents. Herein, we report on the preparation of mono‐, bi‐, and octametallic aluminum complexes through direct chelation of multidentate bis(phosphino)‐2,2‐dimethyl‐1,3‐diamino ligands (Me2C[CH2NH2R2P(O))2]; R = Ph(1), iPr(2), tBu(3). Ligands 1–3 yielded bimetallic complexes with two types of coordination pockets, as well as bimetallic systems with identical coordination environments. In addition to the diversity of structural patterns within the present series, the catalytic performances of [AlR2{κ2‐N,N’,‐(Me2C{CH2NPh2P(O))2}‐(κ2‐O,O’‐AlR2)] (R = Me(4), Et(5), iBu(6)) outperformed that of the monometallic [AlEt2{κ2‐O,O’‐(Me2C(CH2NtBu2P(O))2H} (10), showing controlled and immortal ROP of ε‐CL in the presence of BnOH as co‐initiator. DFT calculations suggest that the primary active site for 4–6 is the N‐Al‐N center. Gaining insight into the underlying principles that lead to high activity and controlled production of PCL in bimetallic systems can help design tailor‐made complexes with enhanced performance.

Copolymerization of β-Butyrolactones into Functionalized Polyhydroxyalkanoates Using Aluminum Catalysts: Influence of the Initiator in the Ring-Opening Polymerization Mechanism.

Within bioplastics, natural poly(3-hydroxybutyrate) (PHB) stands out as fully biocompatible and biodegradable, even in marine environments; however, its high isotacticity and crystallinity limits its mechanical properties and hence its applications. PHB can also be synthesized with different tacticities via a catalytic ring-opening polymerization (ROP) of rac-β-butyrolactone (BBL), paving the way to PHB with better thermomechanical and processability properties. In this work, the catalyst family is extended based on aluminum phenoxy-imine methyl catalyst [AlMeL2], that reveals efficient in the ROP of BBL, to the halogeno analogous complex [AlClL2]. As well, the impact on the ROP mechanism of different initiators is further explored with a particular focus in dimethylaminopyridine (DMAP), a hardly studied initiator for the ROP of BBL. A thorough mechanistic study is performed that evidences the presence of two concomitant DMAP-mediated mechanisms, that lead to either a DMAP or a crotonate end-capping group. Besides, in order to increase the possibilities of PHB post-polymerization functionalization, the introduction of a side-chain functionality is explored, establishing the copolymerization of BBL with β-allyloxymethylene propiolactone (BPLOAll), resulting in well-defined P(BBL-co-BPLOAll) copolymers.

Synthesis and catalytic activity of single-site group V alkoxide complexes for the ring-opening polymerization of ε-caprolactone.

The synthesis, characterization, and ring-opening polymerization (ROP) activity of a family of niobium and tantalum alkoxide catalysts was studied. The final catalysts are made in a two-step synthesis, first by reacting the desired homoleptic metal ethoxide with a phenolketoimine ligand to form a series of synthetic intermediates, followed by reaction with catechol to produce a catalytic platform with a single ethoxide initiator. By using two separate ligands, the electronic properties of the catalyst can be tuned, and the molecular weight of the polymer can be increased. It was found that synthetic intermediates adopted a mer geometry both in solution and in the solid state. This mer geometry was retained for the final catechol derivatives, however in one case, where catechol was substituted for 3-methoxycatechol, the molecule adopted a highly distorted fac geometry. Catalytic ROP activity of the synthetic intermediates and final catechol derivatives with ε-caprolactone was studied through a kinetic analysis. In all seven cases studied the reactions proceeded through the expected coordination-insertion mechanism, following pseudo first-order kinetics and increasing in Mn linearly vs. conversion. The single-initiator catechol derivatives increased the Mn by three times compared to that of the three-initiator synthetic intermediates with little decrease in the overall reaction rate. Both the nature of the ligand and metal were found to impact the rate of reaction in these systems. By switching from an electron donating ligand to an electron withdrawing ligand, the rate was found to nearly double. Tantalum species were faster than their niobium counterparts by ∼3 times in the synthetic intermediates and ∼1.5 times in the catechol derivatives. This observed periodicity supports recent literature findings in this area.

Deconstructable and Chemically Recyclable High-Density Polyethylene (HDPE)-Like Materials Based on Si-O Bonds.

Polyethylene (PE) is the most widely produced synthetic polymer. By installing chemically cleavable bonds into the backbone of PE, it is possible to produce chemically deconstructable PE derivatives; to date, however, such designs have primarily relied on carbonyl- and olefin-related functional groups. Bifunctional silyl ethers (BSEs; SiR2(OR'2)) could expand the functional scope of PE mimics as they possess strong Si-O bonds, excellent oxidative stabilities, and facile chemical tunability. Here, we report BSE-containing high-density polyethylene (HDPE)-like materials synthesized through a one-pot catalytic ring-opening metathesis polymerization (ROMP) and hydrogenation sequence. The crystallinity of these materials can be adjusted by varying the BSE concentration or the steric bulk of the Si-substituents, providing handles to control thermomechanical properties while maintaining the high thermal stability of HDPE. Two methods for chemical recycling of HDPE mimics are introduced, including a circular approach that leverages acid-catalyzed Si-O bond exchange with 1-propanol. Additionally, despite the fact that the starting HDPE mimics were synthesized by chain-growth polymerization (ROMP), we show that it is possible to recover the molar mass and dispersity of recycled HDPE products using step-growth Si-O bond formation or exchange, generating high molecular weight recycled HDPE products with mechanical properties similar to commercial HDPE.

Coordination of ε-Caprolactone to a Cationic Niobium(V) Alkoxide Complex: Fundamental Insight into Ring-Opening Polymerization via Coordination-Insertion.

We report three niobium-based initiators for the catalytic ring-opening polymerization (ROP) of ε-caprolactone, exhibiting good activity and molecular weight control. In particular, we have prepared on the gram-scale and fully characterized a monometallic cationic alkoxo-Nb(V) ε-caprolactone adduct representing, to the best of our knowledge, an unprecedented example of a metal complex with an intact lactone monomer and a functional ROP-initiating group simultaneously coordinated at the metal center. At 80 °C, all three systems initiate the immortal solution-state ROP of ε-caprolactone via a coordination-insertion mechanism, which has been confirmed through experimental studies, and is supported by computational data. Natural bond orbital calculations further indicate that polymerization may necessitate isomerization about the metal center between the alkoxide chain and the coordinated monomer. The observations made in this work are expected to inform mechanistic understanding both of amine tris(phenolate)-supported metal alkoxide ROP initiators, including various highly stereoselective systems for the polymerization of lactides and of coordination-insertion-type ROP protocols more broadly.

One-Pot, Open-Air Synthesis of Flexible and Degradable Multifunctional Polymer Composites with Adhesion, Water Resistance, Self-Healing, Facile Drug Loading, and Sustained Release Properties.

Developing proper wound management via wound dressings represents a global challenge. Ideal wound dressings shall encompass multiple integrated functionalities for variable, complex scenarios; however, this is challenging due to the complex molecular design and synthesis process. Herein, polymer composites, cross-linked poly(styrene oxide-co-hexaphenylcyclotrisiloxane)/crosslinked poly(hexaphenylcyclotrisiloxane) (cP(SO-co-HPCTS)/cPHPCTS) with multiple functionalities are prepared by a one-step, open-air method using catalytic ring-opening polymerization. The introduction of a mobile polymer cP(SO-co-HPCTS) endows the composite with good flexibility and self-healing properties at human body temperature. The hydrophobic groups in the main chain provide hydrophobicity and good water resistance, while the hydroxyl groups contained in the end groups enable good adhesion properties. Drugs can be efficiently loaded by blending and then sustainably release from the polymer composite. The material can rapidly degrade in a tetrahydrofuran solution of tetrabutylammonium fluoride due to its SiOSi bonds. The facile, one-step, open-air synthesis procedure and multiple functional properties integrated into the composites provide good prospects for their extensive application and batch production as wound dressing materials.

Practical Route for Catalytic Ring-Opening Metathesis Polymerization.

Norbornene derivatives are typical monomers for ring-opening metathesis polymerization (ROMP) for synthesizing highly functional polymers. However, the lack of catalytic methods, that is, the lack of readily available chain transfer agents (CTAs) for these monomers has been a significant cost limitation when large-scale syntheses are required. Here, we report commercially available styrene and its derivatives as efficient regioselective CTAs for the catalytic synthesis of metathesis polymers requiring up to 1000 times less ruthenium than in classical ROMP experiments. The molecular weight of the synthesized polymers was controlled by the monomer-to-CTA ratio. Low molecular weight ROMP polymers known for their antimicrobial properties were also synthesized on a gram scale in this report. Polymers were characterized by SEC, 1H NMR spectroscopy, and isotopically resolved MALDI-TOF MS. This approach describes a greener, more cost-effective, and eco-friendly methodology for the preparation of metathesis-based materials on the multigram scale.

Macrochain Transfer Agents for Catalytic Ring-Opening Metathesis Polymerization.

A monosubstituted 1,3-diene derivative attached to a polymer is demonstrated to act as a macrochain transfer agent in catalytic ring-opening metathesis polymerization. PEG- and PLA-based macrochain transfer agents were synthesized in a few steps and were characterized using NMR spectroscopy, size exclusion chromatography (SEC) and matrix-assisted laser desorption/ionization-time-of-flight (MALDI-ToF) mass spectrometry. Poly(l-lactide) based diblock copolymer, poly(ethylene glycol)-based diblock, and triblock (ABA type) copolymers of varied chain lengths were prepared catalytically in a one-pot approach via metathesis polymerization. Block copolymers were characterized by SEC and showed monomodal molecular weight distributions. Moreover, DOSY NMR spectroscopy further proved the block microstructures of the synthesized polymers.

Stereogradient Poly(Lactic Acid) from meso-Lactide/L-Lactide Mixtures.

The production of L-lactide from L-lactic acid involves a substantial formation of meso-lactide as an impurity, and, upon polymerization with the industrial catalyst tin octanoate, results in poly(L-lactic acid) of reduced crystallinity due to stereoerrors randomly distributed along the polymer chains. We describe a new approach wherein, instead of avoiding stereoerrors by removing the meso-lactide prior to polymerization, the stereoerrors in the polymer are tolerated, by crowding them in a stereogradient copolymer. A zirconium complex of an amine tris(phenolate) ligand is found to exhibit very high syndioselectivity in the ring opening polymerization catalysis of meso-lactide at room temperature, and gives rise to stereogradient copolymers in the polymerization of mixtures of meso-lactide/L-lactide in the melt at 180 °C. Relative to the stereo-random copolymers obtained with tin octanoate, the stereogradient copolymers exhibit enhanced crystallinities manifested in lower solubilities and higher melting temperatures and enthalpies.

Stereogradient Poly(Lactic Acid) from meso‐Lactide/L‐Lactide Mixtures

AbstractThe production of L‐lactide from L‐lactic acid involves a substantial formation of meso‐lactide as an impurity, and, upon polymerization with the industrial catalyst tin octanoate, results in poly(L‐lactic acid) of reduced crystallinity due to stereoerrors randomly distributed along the polymer chains. We describe a new approach wherein, instead of avoiding stereoerrors by removing the meso‐lactide prior to polymerization, the stereoerrors in the polymer are tolerated, by crowding them in a stereogradient copolymer. A zirconium complex of an amine tris(phenolate) ligand is found to exhibit very high syndioselectivity in the ring opening polymerization catalysis of meso‐lactide at room temperature, and gives rise to stereogradient copolymers in the polymerization of mixtures of meso‐lactide/L‐lactide in the melt at 180 °C. Relative to the stereo‐random copolymers obtained with tin octanoate, the stereogradient copolymers exhibit enhanced crystallinities manifested in lower solubilities and higher melting temperatures and enthalpies.

Site-Isolated Main-Group Tris(2-pyridyl)borate Complexes by Pyridine Substitution and Their Ring-Opening Polymerization Catalysis

Tris(2-pyridyl)borates are an emerging class of scorpionate ligands, distinguished as exceptionally robust and electron-donating. However, the rapid formation of inert homoleptic complexes with divalent metals has so far limited their catalytic utility. We report site-isolating tris(2-pyridyl)borate ligands, bearing isopropyl, tert-butyl, and mesityl substituents at the pyridine 6-position to suppress the formation of inert homoleptic complexes. These ligands form the first 1:1 complexes between tris(2-pyridyl)borates and Mg2+, Zn2+, or Ca2+, with isopropyl-substituted TpyiPrH showing the most generality. Single-crystal X-ray diffraction analysis of the resulting complexes and comparison to density functional theory (DFT) models showed geometric distortions driven by steric repulsion between the pyridine 6-substituents and the hexamethyldisilazide (HMDS-, -N(SiMe3)2) anion. We show that this steric profile is a feature of the six-membered pyridine ring and contrasts with more established tris(pyrazolyl)borate and tris(imidazoline)borate scorpionate complexes. TpyiPrMg(HMDS) (1) and its zinc analogue are moderately active for the controlled polymerization of l-lactide, ε-caprolactone, and trimethylene carbonate. Furthermore, 1 gives controlled polymerization under more demanding melt-phase polymerization conditions at 100 °C, and block copolymerization of ε-caprolactone and trimethylene carbonate. These results will enable useful catalysis and coordination chemistry studies with tris(2-pyridyl)borates, and characterizes their structural complementarity to more familiar scorpionate ligands.

Tunable and recyclable polyesters from CO2 and butadiene.

Carbon dioxide is inexpensive and abundant, and its prevalence as waste makes it attractive as a sustainable chemical feedstock. Although there are examples of copolymerizations of CO2 with high-energy monomers, the direct copolymerization of CO2 with olefins has not been reported. Here an alternative route to functionalizable, recyclable polyesters derived from CO2, butadiene and hydrogen via an intermediary lactone, 3-ethyl-6-vinyltetrahydro-2H-pyran-2-one, is described. Catalytic ring-opening polymerization of the lactone by 1,5,7-triazabicyclo[4.4.0]dec-5-ene yields polyesters with molar masses up to 13.6 kg mol-1 and pendent vinyl side chains that can undergo post-polymerization functionalization. The polymer has a low ceiling temperature of 138 °C, allowing for facile chemical recycling, and is inherently biodegradable under aerobic aqueous conditions (OECD-301B protocol). These results show that a well-defined polyester can be derived from CO2, olefins and hydrogen, expanding access to new polymer feedstocks that were once considered unfeasible.

Fast-Tracking the l-Lactide Polymerization Activity of Group 4 Metal Complexes of Amine Tris(phenolate) Ligands

Zirconium complexes of amine tris(phenolate) ligands wherein the substituents ortho to the phenolate oxygens are aryl groups are introduced, and their application in the catalysis of ring-opening polymerization of l-lactide at 180 °C is described. Spectroscopic and crystallographic characterization revealed that for ortho-phenyl substituents, bridging dinuclear complexes were obtained, whereas for ortho-mesityl-substituents, fluxional mononuclear complexes were obtained. Melt polymerizations employing catalyst ratios reaching as low as 5 ppm for unpurified l-lactide and 1 ppm for purified l-lactide revealed ultra-high activities for the zirconium complex featuring the mesityl-phenolate substituents, yielding high-molecular-weight stereoerror-free poly(l-lactic acid) that exhibited enhanced stability toward thermal degradation. Slightly lower activities were found for the corresponding hafnium complex and for the zirconium complex featuring the phenyl-phenolate substituents. These catalysts could thus serve as drop-in replacement for the industrially employed stannous octanoate.

Organobase/urea catalyzed ring opening polymerization of 3‐methyl‐1, 4‐dioxan‐2‐one to prepare chemically recyclable poly(ether ester)

AbstractIt is greatly desirable to develop degradable polymers from easily accessible chemicals. In addition to well‐known degradable aliphatic polyesters, poly(ether‐ester) prepared from 1, 4‐dioxan‐2‐one with perfectly alternative ether and ester bonds is a new type of degradable polymer. Due to the low strain of six‐membered 1, 4‐dioxan‐2‐one ring, it remains a challenge to realize the effective and controllable ring‐opening polymerization (ROP) of 1, 4‐dioxan‐2‐one derived monomers despite several catalysts have been attempted. In recent years, the combination of organobase/(thio)urea binary catalytic system has displayed great activity and versatility in the ROP of cyclic esters. Herein, we studied the ROP of 3‐methyl‐1, 4‐dioxan‐2‐one (MDO) using the combinations of various organobases and ureas as catalysts at relatively low temperature. We found that 1, 8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU)/urea pair showed great overall performance in the ROP of MDO, achieving monomer conversion up to 82% within 7 h at −40 °C. Notably, DBU/urea binary catalytic system achieved higher catalytic activity as well as better control over molecular weights and molecular weight distributions compared to previously reported catalysts. The obtained PMDO can completely depolymerize to recover MDO monomer by simple thermolysis, thus established a close‐loop life cycle.

The versatile, functional polyether, polyepichlorohydrin: History, synthesis, and applications

AbstractPolyepichlorohydrin (PECH) is a functional polyether first synthesized in the 1950's by the catalytic ring opening polymerization of epichlorohydrin (ECH), its inexpensive epoxide pre‐cursor. PECH elastomers are used in diverse commercial applications due to their unique combination of properties including low temperature flexibility and heat and oil resistance. PECH holds an interesting place in polymer history as its synthesis led to the discovery of highly effective aluminum‐based catalysts for epoxide polymerizations and a new class of high molecular weight polyether elastomers by an exceptional polymer chemist, Edwin J. Vandenberg. ECH is an ideal feedstock for polymer materials as it is functional, inexpensive, and produced through environmentally friendly means. However, due to the alkyl chloride pendant, polymerizations involving ECH are difficult and limited synthetic advancement has occurred until very recently. This focused review will discuss modern polymerization methods involving ECH while giving a historical perspective on the evolution of these techniques. We will also review applications of ECH‐based polymers and discuss the future development of these materials. We hope to convince the reader to explore ECH‐based materials in their own work.

Advances, Challenges, and Opportunities of Poly(γ-butyrolactone)-Based Recyclable Polymers

The discovery and prosperous growth of synthetic polymers have presented both significant advantages and daunting challenges in the last century. To address the issues of environmental pollution and fossil consumption, recyclable, degradable, and/or biobased polymers have been given much attention in the polymer science community. This viewpoint focuses on the emerging fully chemical recyclable poly(γ-butyrolactone)-based polymers. The breakthrough from nonpolymerizable to efficient polymerization is highlighted by the benefits of the development of a series of catalysis for ring-opening polymerization of γ-butyrolactone. Subsequently, the design of γ-butyrolactone derivatives and synthesis of more recyclable polymers are summarized together with the discussions about the structure and property relationship. Finally, the remaining challenges and promising opportunities are suggested in order to provide insights into the further direction for sustainable polymers.

A New Approach to Developing Long-Acting Injectable Formulations of Anti-HIV Drugs: Poly(Ethylene Phosphoric Acid) Block Copolymers Increase the Efficiency of Tenofovir against HIV-1 in MT-4 Cells.

Despite the world’s combined efforts, human immunodeficiency virus (HIV), the causative agent of AIDS, remains one of the world’s most serious public health challenges. High genetic variability of HIV complicates the development of anti-HIV vaccine, and there is an actual clinical need for increasing the efficiency of anti-HIV drugs in terms of targeted delivery and controlled release. Tenofovir (TFV), a nucleotide-analog reverse transcriptase inhibitor, has gained wide acceptance as a drug for pre-exposure prophylaxis or treatment of HIV infection. In our study, we explored the potential of tenofovir disoproxil (TFD) adducts with block copolymers of poly(ethylene glycol) monomethyl ether and poly(ethylene phosphoric acid) (mPEG-b-PEPA) as candidates for developing a long-acting/controlled-release formulation of TFV. Two types of mPEG-b-PEPA with numbers of ethylene phosphoric acid (EPA) fragments of 13 and 49 were synthesized by catalytic ring-opening polymerization, and used for preparing four types of adducts with TFD. Antiviral activity of [mPEG-b-PEPA]TFD or tenofovir disoproxil fumarate (TDF) was evaluated using the model of experimental HIV infection in vitro (MT-4/HIV-1IIIB). Judging by the values of the selectivity index (SI), TFD exhibited an up to 14-fold higher anti-HIV activity in the form of mPEG-b-PEPA adducts, thus demonstrating significant promise for further development of long-acting/controlled-release injectable TFV formulations.

Boosting Highly Ordered Porosity in Lanthanum Metal-Organic Frameworks for Ring-Opening Polymerization of γ-Butyrolactone

<h2>Summary</h2> γ-butyrolactone (γ-BL), serving as the monomer of biocompatible and recyclable poly(γ-butyrolactone) plastic, faces a giant challenge in ring-opening polymerization (ROP) due to its low strain energy. The ROP of γ-BL is generally achieved under harsh conditions (e.g., high-pressure or gas-protected atmosphere) and is mostly based on homogeneous systems. Here, we synthesize a series of lanthanum metal-organic framework-based porous nanospheres and successfully apply them as heterogeneous catalysts in efficient ROP of γ-BL under mild conditions. Specifically, NNU-mIM-3 presents a yield of 24.6% with low polydispersity distribution centered at 3.6 kDa and the obtained PγBL can be completely and quantitatively recycled into monomers by simple heat treatment. Besides, the ROP catalysis systems have been intensively explored with various imine-based additives, proven to exhibit largely improved performance with PγBL yield of ~50% and Mw of ~8 kDa. This work paves a new way to explore novel heterogeneous catalysts in producing biocompatible and degradable plastics.

Isoselective Polymerization of rac-Lactide by Highly Active Sequential {ONNN} Magnesium Complexes.

The coordination chemistry and the activities in the ring-opening polymerization catalysis of racemic lactide (LA) of magnesium complexes of a series of {ONNN}-type sequential monoanionic ligands are described. All ligands include pyridyl and substituted-phenolate as peripheral groups. The ligands bearing either chiral or meso-bipyrrolidine cores led to single diastereomeric complexes, whereas the ligands bearing a diaminoethane core led to diastereomer mixtures. All {ONNN}Mg-X complexes [X=Cl, HMDS (hexamethyldisilazide)] led to highly active and isoselective catalysts. The complexes bearing the chiral bipyrrolidine core exhibited the highest activities (full consumption of 5000 equiv. of rac-LA at RT within 5 min) and highest isoselectivities (Pm =0.91), as well as a living character. The complexes of the meso-bipyrrolidine based ligands were almost as active and slightly less stereoselective, while those of the diaminoethane based ligands exhibited reduced activities and isoselectivities.

An Innovative Approach for Restoring the Mechanical Properties of Thermoplastic-Matrix Nanocomposite by the Use of Partially Polymerized Cyclic Butylene Terephthalate

This work is focused on the production of a smart material from cyclic butylene-terephthalate (CBT), characterized by the built-in capability to recover its damage, through the catalyzed ring opening polymerization (ROP) of its oligomers; in particular, molten CBT, after filling the damaged zone, can be converted into poly-butylene terephthalate (PBT), thus promoting a join of the broken surfaces and fixing the crack. To obtain a material with self-healing potential, the production of a partially polymerized system is required. For this purpose, two solutions were studied: the first one involved the use of two catalysts with different activation times, whereas the second solution implied the intercalation of the faster catalyst inside the nanoclay lamellae. Since the intercalation allowed slowing the activation of the catalyst, residual CBT can be converted in a second step. Mechanical properties of partially reacted PBT samples and their healing ability were checked by flexural analyses; in order to promote the healing process, samples were notched to simulate partial damage and left in oven for different times and temperatures, to allow the activation of the unreacted catalyst with the consequent ROP of the residual CBT; flexural tests on samples after healing showed a good recovery of mechanical properties.