Ring-opening Polymerization Research Articles

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.

Tailoring the Structure-Property Relationship of Ring-Opened Metathesis Copolymers for CO2-Selective Membranes.

In this work, we explore the use of ring-opening metathesis polymerization (ROMP) facilitated by a second-generation Grubbs catalyst (G2) for the development of advanced polymer membranes aimed at CO2 separation. By employing a novel copolymer blend incorporating 4,4'-oxidianiline (ODA), 1,6-hexanediamine (HDA), 1-adamantylamine (AA), and 3,6,9-trioxaundecylamine (TA), along with a CO2-selective poly(ethylene glycol)/poly(propylene glycol) copolymer (Jeffamine2003) and polydimethylsiloxane (PDMS) units, we have synthesized membranes under ambient conditions with exceptional CO2 separation capabilities. The strategic inclusion of PDMS, up to a 20% composition within the PEG/PPG matrix, has resulted in copolymer membranes that not only surpass the 2008 upper limit for CO2/N2 separation but also meet the commercial targets for CO2/H2 separation. Comprehensive analysis reveals that these membranes adhere to the mixing rule and exhibit percolation behavior across the entire range of compositions (0-100%), maintaining robust antiplasticization performance even under pressures up to 20 atm. Our findings underscore the potential of ROMP in creating precisely engineered membranes for efficient CO2 separation, paving the way for their application in large-scale environmental and industrial processes.

From health supplement to versatile monomer: Radical ring-opening polymerization and depolymerization of α-lipoic acid

The radical ring-opening polymerization (rROP) of α-lipoic acid (LA) and its derivatives represents a synthetically accessible, efficient, and scalable strategy to impart degradability into functional copolymers. This review highlights recent advances in the design of sustainable materials containing LA through rROP driven by heat and/or light.

Amphiphilic polymer Co-networks based on cross-linked tetra-PEG-b-PCL star block copolymers

A new class of AB4-type amphiphilic polymer co-networks (ACN) was prepared by hetero-complementary 2-(4-nitrophenyl)-benzoxazinone/amine end group cross-linking chemistry in dimethyl sulfoxide (DMSO). For this purpose, a well-defined star block copolymer (tetra-PEG-b-PCL) consisting of a hydrophilic tetra-arm PEG core (Mn ∼ 5 kg mol−1) and hydrophobic PCL wings with a total molar mass of Mn ∼ 10 kg mol−1 was synthesized by ring-opening polymerization (ROP). This tetra-PEG-b-PCL star block copolymer was functionalized either with 2-(4-nitrophenyl)-benzoxazinone or with amino terminal groups. The ACN synthesis was carried out by conversion of these two star block copolymers. The overlap concentration of c* ∼76 g L−1 determined by viscosity measurements of both stars showed no significant temperature dependence. The network syntheses carried out at different concentrations (0.5 c* to 2.5 c*) resulted in conversion degrees in the range of p ≈ 95 % or higher as detected by HR MAS NMR spectroscopy. As in previous work on the synthesis of A4B4 networks using the same cross-linking chemistry, deviations from the expected network structure (increased proportion of double links between two stars) were detected also here by multi quantum NMR spectroscopy. The expected environmentally sensitive behavior of the ACNs was confirmed in terms of their equilibrium swelling in solvents of different quality to PEG and PCL. The scaling of the swelling and viscoelasticity data as a function of preparation concentration showed deviations from the expectations of a perfectly cross-linked star polymer network. Finally, a two-step gelation process was observed by rheology at 30 °C in DMSO, which is related to associations between the 2-(4-nitrophenyl)-benzoxazinone groups surrounded by PCL blocks that become apparent on the time scale of rheology when the molar mass is increased as a result of cross-linking.

Synthesis, Structural Characterization of Substituted Phenoxyimine Based Ti(IV) Complexes for Ring Opening Polymerization and DFT Studies

AbstractA series of 4 new titanium complexes bearing phenoxyimine ligands that differ in their steric and electronic properties have been synthesized and investigated for the polymerization of ethylene and rac‐lactide. X‐ray crystal structures of these catalysts reveal compounds 1–3 exhibit distorted octahedral geometry while complex 4 shows distorted trigonal bipyramidal. The substituents on the phenoxyimine framework have a profound influence on the catalytic activities of these compounds in the polymerization reactions. All four complexes afforded polylactide with a heterotactic bias in ring opening polymerization of rac‐lactide. In addition to this, density functional theory calculations using (B3LYP) with the 6‐311++G (d, p) basis set and no constraints were used while doing geometry optimizations and compared with experimental results. Hirshfeld surface analysis, MEP and Mulliken charge also reported an unexpected relationship between the nitrogen, oxygen on the ligands, titanium isopropoxide, and good relation between the experimental findings.

Converting inorganic sulfur into degradable thermoplastics and adhesives by copolymerization with cyclic disulfides

Converting elementary sulfur into sulfur-rich polymers provides a sustainable strategy to replace fossil-fuel-based plastics. However, the low ring strain of eight-membered rings, i.e., S8 monomers, compromises their ring-opening polymerization (ROP) due to lack of an enthalpic driving force and as a consequence, poly(sulfur) is inherently unstable. Here we report that copolymerization with cyclic disulfides, e.g., 1,2-dithiolanes, can enable a simple and energy-saving way to convert elementary sulfur into sulfur-rich thermoplastics. The key strategy is to combine two types of ROP—both mediated by disulfide bond exchange—to tackle the thermodynamic instability of poly(sulfur). Meanwhile, the readily modifiable sidechain of the cyclic disulfides provides chemical space to engineer the mechanical properties and dynamic functions over a large range, e.g., self-repairing ability and degradability. Thus, this simple and robust system is expected to be a starting point for the organic transformation of inorganic sulfur toward sulfur-rich functional and green plastics.

Polymerization/Depolymerization-Induced Self-Assembly under Coupled Equilibria of Polymerization with Self-Assembly.

Depolymerization breaks down polymer chains into monomers like unthreading beads, attracting more attention from a sustainability standpoint. When polymerization reaches equilibrium, polymerization and depolymerization can reversibly proceed by decreasing and increasing the temperature. Here, we demonstrate that such dynamic control of a growing polymer chain in a selective solvent can spontaneously modulate the self-assembly of block copolymer micellar nano-objects. Compared to polymerization-induced self-assembly (PISA), where irreversible growth of a solvophobic polymer block from the end of a solvophilic polymer causes micellization, polymerization/depolymerization-induced self-assembly presented in this study allows us to reversibly regulate the packing parameter of the forming block copolymer and thus induce reversible morphological transitions of the nano-objects by temperature swing. Under the coupled equilibria of polymerization with self-assembly, we found that demixing of the growing polymer block in a more selective solvent entropically facilitates depolymerization at a substantially lower temperature. Taking ring-opening polymerization of δ-valerolactone initiated from the hydroxyl-terminated poly(ethylene oxide) as a model system, we show that polymerization/depolymerization/repolymerization leads to reversible morphological transitions, such as rod-sphere-rod and fiber-rod-fiber, during the heating and cooling cycle and accompanied by changes in macroscopic properties such as viscosity, suggesting their potential as dynamic soft materials.

A four-in-one multifunctional self-assembly hydrogel composed of natural drugs for repairing myocardial infarction

To meet the multiple demands of myocardial repair, it would be a novel strategy for myocardial repair if multiple drugs could be constructed into an integrated multifunctional drug formulation. In this study, four drugs with different functions (thioctic acid with antioxidant effects, quercetin with anti-inflammatory and antioxidant effects, arginine with pro-angiogenic effects, and Mn2+ with imaging functions) were selected to construct a four-in-one injectable hydrogel (thioctic acid-arginine-quercetin-Mn2+) through chemical bonding and supramolecular interactions. First, thioctic acid polymerized to a redox-sensitive degradable polymer—poly(thioctic acid) containing disulfide bonds in the main chains through ring-opening polymerization. Quercetin was conjugated to the main chain of the poly(thioctic acid) molecules via thiyl radical-polyphenol Michael addition. Arginine cross-linked the carboxyl groups side chains of the poly(thioctic acid) molecules through hydrogen bonding. Mn2+ further cross-linked the carboxyl groups' side chains of the poly(thioctic acid) molecules through ionic bonding. The hydrogel has antioxidant properties, promotes neovascularization, inhibits inflammatory, improves intracellular Ca2+ overload and mitochondrial dysfunction, protects adenosine triphosphatase (ATPase) activity, and maintains intracellular energy supply, which can reduce the size of myocardial infarcts, and improves cardiac function. This construction method of preparing integrated multifunctional hydrogels from natural drugs will provide a new therapeutic strategy for myocardial repair.

Photoactivatable poly(2-oxazoline)s enable antifouling hydrogel membrane coatings

In recent years, hydrophilic poly(2-oxazoline)s have been examined as an alternative polymer to poly(ethylene glycol) (PEG) with added stability and chemical versatility. They show excellent anti-fouling properties and, like PEG, are of interest in many fields where bio-inertness or anti-adhesiveness are important such as for medical devices, tissue engineering, biosensors, or drug delivery carriers. Surprisingly few studies have utilized this polymer class for the preparation of anti-fouling membranes. Here we describe a new termination reaction of the living cationic ring-opening polymerization of 2-oxazolines in which a benzophenone group is introduced as a photoactivatable terminal head group of poly(2-oxazoline)s. Using 4-vinylbenzyl chloride as initiator, heterotelechelic poly(2-methyl-2-oxazoline) (PMOXA) macromonomers were synthesized and copolymerized with hydroxyl-functional PMOXA macromonomers to yield photoactivatable PMOXA-based prepolymer bottle brushes. Likewise, star-PMOXAs were synthesized by using a trifunctional initiator. Photoactivatable PMOXA prepolymers allowed us to readily form anti-fouling hydrogels by a simple and versatile CH-insertion cross-linking (CHic) process. Hydrogels were applied to poly(ether sulfone) ultrafiltration membranes as pore coating and the pure water permeance (PWP) was investigated as a function of hydrogel architecture and cross-link density. Anti-fouling hydrogel pore-coated membranes having PWPs on the order of hundred kg·m−2·h−1·bar−1 were obtained.

Ring-Opening Polymerization of Cyclohexene Oxide and Cycloaddition with CO2 Catalyzed by Amine Triphenolate Iron(III) Complexes.

A series of novel amine triphenolate iron complexes were synthesized and characterized using UV, IR, elemental analysis, and high-resolution mass spectrometry. These complexes were applied to the ring-opening polymerization (ROP) of cyclohexene oxide (CHO), demonstrating excellent activity (TOF > 11050 h-1) in the absence of a co-catalyst. In addition, complex C1 maintained the dimer in the presence of the reaction substrate CHO, catalyzing the ring-opening polymerization of CHO to PCHO through bimetallic synergy. Furthermore, a two-component system consisting of iron complexes and TBAB displayed the ability to catalyze the reaction of CHO with CO2, resulting in the formation of cis-cyclic carbonate with high selectivity. Complex C4 exhibited the highest catalytic activity, achieving 80% conversion of CHO at a CHO/C4/TBAB molar ratio of 2000/1/8 and a CO2 pressure of 3 MPa for 16 h at 100 °C, while maintaining >99% selectivity of cis-cyclic carbonates, which demonstrated good conversion and selectivity.

In Vitro Biocompatibility and Endothelial Permeability of Branched Polyglycidols Generated by Ring-Opening Polymerization of Glycidol with B(C6F5)3 under Dry and Wet Conditions.

Polyglycidol or polyglycerol (PG), a polyether widely used in biomedical applications, has not been extensively studied in its branched cyclic form (bcPG), despite extensive research on hyperbranched PG (HPG). This study explores the biomedical promise of bcPG, particularly its ability to cross the blood-brain barrier (BBB). We evaluate in vitro biocompatibility, endothelial permeability, and formation of branched linear PG (blPG) as topological impurities in the presence of water. Small angle X-ray scattering in solution revealed a fractal dimension of approximately two for bcPG and the mixture bc+blPG, suggesting random branching. Comparisons of cytotoxicity and endothelial permeability between bcPG, bc+blPG, and HPG in a BBB model using hCMEC/D3 cells showed different biocompatibility profiles and higher endothelial permeability for HPG. bcPG showed a tendency to accumulate around cell nuclei, in contrast to the behavior of HPG. This study contributes to the understanding of the influence of polymer topology on biological behavior.

Reprocessability in Engineering Thermosets Achieved Through Frontal Ring-Opening Metathesis Polymerization.

While valued for their durability and exceptional performance, crosslinked thermosets are challenging to recycle and reuse. Here, inherent reprocessability in industrially relevant polyolefin thermosets is unveiled. Unlike prior methods, this approach eliminates the need to introduce exchangeable functionality to regenerate the material, relying instead on preserving the activity of the metathesis catalyst employed in the curing reaction. Frontal ring-opening metathesis polymerization (FROMP) proves critical to preserving this activity. Conditions controlling catalytic viability are explored to successfully reclaim performance across multiple generations of material, thus demonstrating long-term reprocessability. This straightforward and scalable remolding strategy is poised for widespread adoption. Given the anticipated growth in polyolefin thermosets, these findings represent an important conceptual advance in the pursuit of a fully circular lifecycle for thermoset polymers.

Polypeptide- and Protein-Based Conjugate Nanoparticles via Aqueous Ring-Opening Polymerization-Induced Self-Assembly (ROPISA).

Protein-polymer conjugates and polymeric nanomaterials hold great promise in many applications including biomaterials, medicine, or nanoelectronics. In this work, the first polymerization-induced self-assembly (PISA) approach performed in aqueous medium enabling protein-polymer conjugates and nanoparticles entirely composed of amino acids is presented by using ring-opening polymerization (ROP). It is indeed shown that aqueous ring-opening polymerization-induced self-assembly (ROPISA) can be used with protein or peptidic macroinitiators without prior chemical modification and afford the simple preparation of nanomaterials with protein-like property, for example, to implement biomimetic thermoresponsivity in drug delivery.

Dextran Macroinitiator for Synthesis of Polysaccharide-b-Polypeptide Block Copolymers via NCA Ring-Opening Polymerization.

Synthesis of polysaccharide-b-polypeptide block copolymers represents an attractive goal because of their promising potential in delivery applications. Inspired by recent breakthroughs in N-carboxyanhydride (NCA) ring-opening polymerization (ROP), we present an efficient approach for preparation of a dextran-based macroinitiator and the subsequent synthesis of dextran-b-polypeptides via NCA ROP. This is an original approach to creating and employing a native polysaccharide macroinitiator for block copolymer synthesis. In this strategy, regioselective (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) oxidation of the sole primary alcohol located at the C-6 position of the monosaccharide at the nonreducing end of linear dextran results in a carboxylic acid. This motif is then transformed into a tetraalkylammonium carboxylate, thereby generating the dextran macroinitiator. This macroinitiator initiates a wide range of NCA monomers and produces dextran-b-polypeptides with a degree of polymerization (DP) of the polypeptide up to 70 in a controlled manner (Đ < 1.3). This strategy offers several distinct advantages, including preservation of the original dextran backbone structure, relatively rapid polymerization, and moisture tolerance. The dextran-b-polypeptides exhibit interesting self-assembly behavior. Their nanostructures have been investigated by dynamic light scattering (DLS) and transmission electron microscopy (TEM), and adjustment of the structure of block copolymers allows self-assembly of spherical micelles and worm-like micelles with varied diameters and aspect ratios, revealing a range of diameters from 60 to 160 nm. Moreover, these nanostructures exhibit diverse morphologies, including spherical micelles and worm-like micelles, enabling delivery applications.

Effect of Keratin Waste on Poly(ε-Caprolactone) Films: Structural Characterization, Thermal Properties, and Keratinocytes Viability and Proliferation Studies

Keratin extracted (KE) from chicken feathers was used for the production of composite films comprising poly(ε-caprolactone) (PCL) and keratin (PCL/KE films). The process involved the extraction of keratin from chicken feathers using a 0.1 M NaOH solution, followed by characterization via sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). The PCL was synthesized through the ring-opening polymerization (ROP) of ε-caprolactone (ԑ-CL) with Sn(Oct)2 as a catalyst. Films were prepared via solvent casting, including pure PCL films and those enriched with different weight percentages of KE (10%, 15%, 25%, and 30%). The films were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TG), and scanning electron microscopy (SEM). SEM analysis revealed a more uniform incorporation of KE within the PCL matrix in the case of the 15% keratin-enriched film (PCL/KE15) as compared to other keratin percentages. The thermal analysis showed a positive influence of keratin on the thermal stability of the films. Keratinocytes viability and proliferation tests on the PCL/KE15 film demonstrated compatibility with cells. Collectively, these results hold relevance for potential biomedical applications of PCL/KE films.

The effect of polymer with tunable alkyl spacers on the microstructure of amphoteric membrane for vanadium redox flow battery (VRB)

Amphoteric membranes, as promising candidates for VRBs, have attracted more attention. The side-chain-type polymers go far towards improving ion exchange capacity and further enhancing ion conductivity. A kind of Amphoteric ion exchange membranes (AIEMs) with different alkyl chain lengths (C2, C6, and C12 spacers) were synthesized by using ring-opening metathesis polymerization (ROMP). In addition, the interactions between N-containing groups with positively charged and -SO3- groups prevent swelling and vanadium crossover. The microphase separation structure through side chain induction was regulated, to respond to the ionic mobility of the membrane. The effect of the spacer lengths on the ion selectivity of AIEMs is investigated. In addition, the size and matrix of the constructed ion channel were calculated by using coarse-grained molecular dynamics (CGMD) simulation, which further verified the experiment.

Weak Interaction Activates Esters: Reconciling Catalytic Activity and Turnover Contradiction by Tailored Chalcogen Bonding.

The activation of esters by strong Lewis acids via the formation of covalent adducts is a classic strategy to give reactivity; however, this approach frequently incurs limited turnover due to the low efficiency in the dissociation of catalyst from a stable catalyst-product complex. While the use of some weak interaction catalysts that can easily dissociate from any bonding complexes in the reaction system would solve this catalyst turnover problem, the poor catalytic activity in the ester activation that can be provided by these noncovalent forces in turn sets up a formidable challenge. Herein, we describe the activation and catalytic transformation of esters by weak interactions, which provides a promising platform to reconcile the catalytic activity and turnover problems. Several tailored chalcogen-bonding catalysts were developed for the activation of esters, enabling achieving several inherently low reactive Diels-Alder reactions as well as the ring-opening polymerization of lactones through weak chalcogen bonding interactions. This supramolecular catalysis approach is particularly highlighted by its capability to promote some uncommon Diels-Alder reactions involving using dienes bearing electron-withdrawing groups coupled by α,β-unsaturated ester as dienophiles and substrate incorporating competitive Lewis basic sites, in which typical strong Lewis acids showed low catalytic efficiency, while representative hydrogen and halogen bonding catalysts were inactive.

Remarkable impact of chain backbone on the performance of Poly(norbornene derivatives)-based anion exchange membranes

Chemical stability and the trade-off between ion conductivity and dimensional stability are two primary challenges for the development of suitable anion exchange membranes (AEMs). Herein, a series of non-crosslinked poly(norbornene derivatives)-based AEMs containing a bulky steric hindrance hydrophobic arylene substituent were prepared by vinyl addition polymerization (VAP), ring-opening metathesis polymerization (ROMP), and ROMP followed post-hydrogenation, respectively. Compared with ROMP and hydrogenated type membranes, VAP-type membranes, especially the VAP-N-50, exhibited excellent dimensional stability with limited swelling ratio (SR = 27.9 %) while higher water uptake (WU = 213.8 %) at 80 °C, which is attributed to its rigid VAP-type cyclic chain backbone. Microtopography study demonstrated the existence of nanoscale phase separation in VAP-type AEMs and its association with water uptake and swelling behavior. VAP-N-60 showed excellent hydroxide conductivity up to 105.5 mS cm−1 at 80 °C, while exhibited superior alkaline stability that was not found in ROMP-type membrane ROMP-N-50 and the hydrogenated-type membrane H-ROMP-N-50. After being immersed in 2 M NaOH solution at 80 °C for 1200 h, the hydroxide conductivity loss of VAP-N-60 was only 3.0 %. Furthermore, a H2/O2 single cell using VAP-N-50 membrane achieved the highest peak power density of 722 mW cm−2 at 60 °C without back pressure.

Curing kinetics and plugging mechanism of high strength curable resin plugging material

Lost circulation, a recurring peril during drilling operations, entails substantial loss of drilling fluid and dire consequences upon its infiltration into the formation. As drilling depth escalates, the formation temperature and pressure intensify, imposing exacting demands on plug materials. In this study, a kind of controllable curing resin with dense cross-network structure was prepared by the method of solution stepwise ring-opening polymerization. The resin plugging material investigated in this study is a continuous phase material that offers effortless injection, robust filling capabilities, exceptional retention, and underground curing or crosslinking with high strength. Its versatility is not constrained by fracture-cavity lose channels, making it suitable for fulfilling the essential needs of various fracture-cavity combinations when plugging fracture-cavity carbonate rocks. Notably, the curing duration can be fine-tuned within the span of 3–7 h, catering to the plugging of drilling fluid losing of diverse fracture dimensions. Experimental scrutiny encompassed the rheological properties and curing behavior of the resin plugging system, unraveling the intricacies of the curing process and establishing a cogent kinetic model. The experimental results show that the urea-formaldehyde resin plugging material has a tight chain or network structure. When the concentration of the urea-formaldehyde resin plugging system solution remains below 30%, the viscosity clocks in at a meager 10 mPa·s. Optimum curing transpires at 60 °C, showcasing impressive resilience to saline conditions. Remarkably, when immersed in a composite saltwater environment containing 50000 mg/L NaCl and 100000 mg/L CaCl2, the urea-formaldehyde resin consolidates into an even more compact network structure, culminating in an outstanding compressive strength of 41.5 MPa. Through resolving the correlation between conversion and the apparent activation energy of the non-isothermal DSC curing reaction parameters, the study attests to the fulfillment of the kinetic equation for the urea-formaldehyde resin plugging system. This discerning analysis illuminates the nuanced shifts in the microscopic reaction mechanism of the urea-formaldehyde resin plugging system. Furthermore, the pressure bearing plugging capacity of the resin plugging system for fractures of different sizes is also studied. It is found that the resin plugging system can effectively resident in parallel and wedge-shaped fractures of different sizes, and form high-strength consolidation under certain temperature conditions. The maximum plugging pressure of resin plugging system for parallel fractures with outlet size 3 mm can reach 9.92 MPa, and the maximum plugging pressure for wedge-shaped fractures with outlet size 5 mm can reach 9.90 MPa. Consequently, the exploration and application of urea-formaldehyde resin plugging material precipitate a paradigm shift, proffering novel concepts and methodologies in resolving the practical quandaries afflicting drilling fluid plugging.

Upgrading of thermosets and composites via sequential frontal ring-opening metathesis polymerization and radical reactions

Upgrading of thermosets and composites via sequential frontal ring-opening metathesis polymerization and radical reactions