Anionic Ring-opening Polymerization Research Articles

Ring-opening polymerization of six-membered cyclic hybrid dimers composed of an oxoester and thioester

AbstractThree cyclic oxoester-thioester hybrid monomers, 1 (3-methyl-1,4-oxathiane-2,5-dione), 2 (6-methyl-1,4-oxathiane-2,5-dione), and 3 (3,6-dimethyl-1,4-oxathiane-2,5-dione), were studied for anionic and cationic ring-opening polymerizations. These monomers are six-membered cyclic cross-dimers corresponding to combinations of glycolic and lactic acids with their thiol analogs. Anionic polymerizations using thiol as the initiator and 2,6-lutidine as the base catalyst were successful for the chemoselective cleavage of the thioester with the thiol propagating end. The polymerizability increased in the order of 3 < 1 < 2, which was in good agreement with the increasing ring strain order evaluated by Density Functional Theory calculations. The living character, to some extent, was suggested by the postpolymerization reactions, which involved a two-stage feed of the monomers and a thiol-ene terminal coupling reaction to form a block copolymer with PEG. Additionally, it was found that the polymerization took place in 2,6-lutidine without a thiol initiator and produced macrocyclic polymers. The cationic polymerizations took place with the aid of CF3SO3H and benzyl alcohol but involved side reactions with low chemoselective ring cleavage. The thioester unit caused the polymers to exhibit a lower Tg with greater thermal and photo degradability.

Mastering Macromolecular Architecture by Controlling Backbiting Kinetics during Anionic Ring-Opening Polymerization

Mastering Macromolecular Architecture by Controlling Backbiting Kinetics during Anionic Ring-Opening Polymerization

New perspectives on poly(lauryllactam) PA12: Optimization of process parameters for AROP of ω‐lauryllactam

AbstractThis study focuses on how catalyst concentration, activator concentration, and initial polymerization temperature impact in‐situ anionic ring‐opening polymerization (AROP) of ω‐lauryllactam. Catalyst and activator roles are fulfilled by NaH and toluene‐2,4‐diisocyanate (TDI), respectively, with varying catalyst/activator ratios to assess the influence of a bifunctional activator on the polymerization process. The materials produced undergo a thorough analysis, with a specific emphasis on solidification time. The examination extends to scrutinizing how different concentrations of catalyst/activator and polymerization temperatures affect crucial physical and chemical parameters. The study identifies NaH‐6 mol%/TDI‐3 mol% as the optimal formulation for solidification among the three explored temperatures. Notably, at 180 and 200°C, PA12 exhibits enhanced monomer conversion when a catalyst/activator ratio of 1.7 or 2 is applied. These findings underscore the significant impact of the catalyst/activator ratio and their individual concentrations on the polymer's final properties. This influence extends to factors such as crystallinity, polymer chain regularity, and dynamic mechanical properties. Additionally, the experimental conditions utilized for anionic polymerization are observed to shape the characteristics of PA12.

Coordinative Double Hydrophilic All-Polyether Micelles for pH-Responsive Delivery of Cisplatin.

Despite its widespread use in the treatment of numerous cancers, the use of cisplatin still raises concerns about its high toxicity and limited selectivity. Consequently, the necessity arises for the development of an effective drug delivery system. Here, we present an effective approach that introduces a double hydrophilic block copolyether for the controlled delivery of cisplatin. Specifically, poly(ethylene glycol)-block-poly(glycidoxy acetic acid) (mPEG-b-PGA) was synthesized via anionic ring-opening polymerization using the oxazoline-based epoxide monomer 4,4-dimethyl-2-oxazoline glycidyl ether, followed by subsequent acidic deprotection. The coordinative metal-ligand interaction between cisplatin and the carboxylate group within the PGA block facilitated the formation of micelles from the double hydrophilic mPEG-b-PGA copolyether. Cisplatin-loaded polymeric micelles had a high loading capacity, controlled pH-responsive release kinetics, and high cell viability. Furthermore, in vitro biological assays revealed cellular apoptosis induced by the cisplatin-loaded micelles. This study thus successfully demonstrates the potential use of double hydrophilic block copolyethers as a versatile platform for biomedical applications.

One-step synthesis of cyclodextrin-based fluorescent hyperbranched polymer as type I photosensitizer for effective photodynamic therapy

Photodynamic therapy (PDT) is a promising treatment regime for cancer therapy with some advantages such as minimal invasiveness, high spatiotemporal selectivity, and negligible drug resistance. Developing Type I photosensitizer (PS) is a viable strategy to overcome the limitations of conventional O2-dependent Type Ⅱ PS, whereas there are still significant challenges. Herein, we report the synthesis of β-cyclodextrin-based fluorescent hyperbranched polymer (β-CD-HPG-DEP) through a one-step anionic ring-opening polymerization between β-cyclodextrin (β-CD), glycidol and a fluorescent molecule DEP. The potential utilization of β-CD-HPG-DEP as the agent for cancer phototheranostics was also investigated in detail. The results demonstrated that β-CD-HPG-DEP possesses excellent water dispersibility, good biocompatibility, high reactive oxygen species (ROS) generation efficiency mainly via Type I mechanism, and extraordinary fluorescence imaging capability. Meanwhile, β-CD-HPG-DEP has great potential to serve as drug delivery vehicle since the cyclodextrin unit has many hydroxyl groups, thus providing a promising strategy for designing and fabrication of multifunctional theranostics. Considering the simple synthesis route, ready designability and multifunctional potential of anionic ring-opening polymerization, as well as good biocompatibility of resultant polymer, we believe the strategy developed in this work could also be a rational route to synthesize multifunctional composites for various biomedical applications.

Power of the Disulfide Bond: An Ideal Random Copolymerization of Biodegradable Redox-Responsive Hyperbranched Polyglycerols.

The development of copolymerization techniques that can randomly incorporate biodegradable moieties into the hyperbranched polyglycerol backbone is an option to prevent its bioaccumulation in vivo. In this study, redox-responsive and biocompatible hyperbranched polyglycerol copolymers of glycidol and 1,4,5-oxadithiepan-2-one were synthesized with an adjustable molecular weight and a defined disulfide bond content through anionic and coordination-insertion ring-opening polymerization. A truly random incorporation of the monomers was achieved under both copolymerization mechanisms. The copolymers were further characterized in terms of their aggregation behavior in solution, degradability, in vitro cell viability, and blood compatibility for potential future biomedical applications. Transmission electron microscopy revealed that the copolymer assembled into nanoparticles with a size range of 20 nm. The copolymers underwent degradation when incubated with two different reducing agents, resulting in smaller fragments of the polymer with thiol end groups. The copolymers demonstrated good biocompatibility, making them suitable for further investigation in biomedical applications.

Contrasting Roles of Counterions in Anionic Ring-Opening Polymerization Mediated by Heterocycle Organocatalysts

Contrasting Roles of Counterions in Anionic Ring-Opening Polymerization Mediated by Heterocycle Organocatalysts

Designing Polymer Electrolytes via Ring‐Opening Polymerization for Advanced Lithium Batteries

AbstractReplacing liquid electrolytes with solid‐state polymer electrolytes (SPEs) can solve the safety hazards of Li metal batteries (LMBs) while increasing their energy density. However, there has been limited success so far in preparing advanced SPEs with controllable molecular structure and chemical composition, posing great obstacles to further promoting its application in LMBs. Recently, ring‐opening polymerization (ROP), including cationic ROP, anionic ROP, and ring‐opening metathesis polymerization, has become a dazzling new star in achieving SPEs due to its mild polymerization conditions and controllable chemical composition (molecular structure, functional group), etc. Besides, there is no small molecule released during the polymerization process, which means reduced interfacial side reaction. Hence, in this review, the merits of ROP in preparing SPEs and its mechanism as well as interfering factors, etc are evaluated from the perspective of synthetic chemistry. Furthermore, the review focuses on outlining the existing cases related to ROP as much as possible and summarize them from different ring structures (from triple ring to multivariate ring) and polymerization methods, hoping to provide a comprehensive understanding and serve as strategic guidance for designing high‐performance SPEs. Challenges and opportunities regarding this burgeoning field are also discussed at the end.

Heterotelechelic Silicones: Facile Synthesis and Functionalization Using Silane-Based Initiators.

The synthetic utility of heterotelechelic polydimethylsiloxane (PDMS) derivatives is limited due to challenges in preparing materials with high chain-end fidelity. In this study, anionic ring-opening polymerization (AROP) of hexamethylcyclotrisiloxane (D3) monomers using a specifically designed silyl hydride (Si-H)-based initiator provides a versatile approach toward a library of heterotelechelic PDMS polymers. A novel initiator, where the Si-H terminal group is connected to a C atom (H-Si-C) and not an O atom (H-Si-O) as in traditional systems, suppresses intermolecular transfer of the Si-H group, leading to heterotelechelic PDMS derivatives with a high degree of control over chain ends. In situ termination of the D3 propagating chain end with commercially available chlorosilanes (alkyl chlorides, methacrylates, and norbornenes) yields an array of chain-end-functionalized PDMS derivatives. This diversity can be further increased by hydrosilylation with functionalized alkenes (alcohols, esters, and epoxides) to generate a library of heterotelechelic PDMS polymers. Due to the living nature of ring-opening polymerization and efficient initiation, narrow-dispersity (Đ < 1.2) polymers spanning a wide range of molar masses (2-11 kg mol-1) were synthesized. With facile access to α-Si-H and ω-norbornene functionalized PDMS macromonomers (H-PDMS-Nb), the synthesis of well-defined supersoft (G' = 30 kPa) PDMS bottlebrush networks, which are difficult to prepare using established strategies, was demonstrated.

Non-Isothermal Crystallization Kinetics of Polyamide 6/Graphene Nanoplatelets Nanocomposites Obtained via In Situ Polymerization: Effect of Nanofiller Size.

Thermoplastic resin transfer molding (T-RTM) technology was applied to synthesize graphene nanoplatelets-based nanocomposites via anionic ring-opening polymerization (AROP). Polyamide 6 (PA6) was obtained by AROP and was used as the polymeric matrix of the developed nanocomposites. The non-isothermal crystallization behavior of PA6 and nanocomposites was analyzed by differential scanning calorimetry (DSC). Nanocomposites with 0.5 wt.% of graphene nanoplatelets (GNPs) with two different diameter sizes were prepared. Results have shown that the crystallization temperature shifted to higher values in the presence of GNPs. This behavior is more noticeable for the nanocomposite prepared with smaller GNPs (PA6/GN). The crystallization kinetic behavior of all samples was assessed by Avrami and Liu's models. It was observed that GNPs increased the crystallization rate, thus revealing a nucleating ability, and also validated the reduction of half-time crystallization values. Such tendency was also supported by the lower activation energy values determined by Friedman's method.

The degradation during recycling of polyamide 6 produced by anionic ring-opening polymerization of ε-caprolactam

As the plastics industry continues to grow, the amount of plastic waste is also increasing. The European Union is controlling plastic waste through various regulations, focusing primarily on recyclability. A good alternative to traditional thermoset composites is thermoplastic polyamide 6 composites produced by Thermoplastic Resin Transfer Molding (T-RTM). Polyamide 6 has high strength and is produced by in-situ anionic ring-opening polymerization in T-RTM. Products made with this technology can replace traditional thermoset composites in many areas, which greatly increases recyclability. In this paper, the recyclability of the high molecular weight polyamide 6 matrix material of T-RTM composites is investigated. Products were mechanically recycled and then processed by injection molding. Thermal, mechanical and rheological properties of the samples were compared with the properties of the original product, as well as a general injection molding–grade PA6. Results show that the parts prepared with this innovative technology can be mechanically recycled and reprocessed by injection molding without a processing aid. After reprocessing, a significant reduction in properties is observed due to degradation, but the properties of the resulting product are in good agreement with those of a conventional commercially available injection molding grade PA6 material.

Anionic ring-opening polymerization of functional epoxide monomers in the solid state

Despite recent advancements in mechanochemical polymerization, understanding the unique mechanochemical reactivity during the ball milling polymerization process still requires extensive investigations. Herein, solid-state anionic ring-opening polymerization is used to synthesize polyethers from various functional epoxide monomers. The critical parameters of the monomers are investigated to elucidate the unique reactivity of ball milling polymerization. The controllable syntheses of the desired polyethers are characterized via NMR, GPC, and MALDI-ToF analyses. Interestingly, bulky monomers exhibit faster conversions in the solid-state in clear contrast to that observed for solution polymerization. Particularly, a close linear correlation is observed between the conversion of the ball milling polymerization and melting point of the functional epoxide monomers, indicating melting point as a critical predictor of mechanochemical polymerization reactivity. This study provides insights into the efficient design and understanding of mechanochemical polymerization.

Living/Controlled Anionic Polymerization of Glycolide in Fluoroalcohols: Toward Sustainable Bioplastics.

Ring-opening polymerization (ROP) is a promising approach to accessing well-defined polyesters with superior (bio)degradability and recyclability. However, the living/controlled polymerization of glycolide (GL), a well-known sustainable monomer derived from carbon monoxide/dioxide, has never been reported due to the extremely low solubility of its polymer in common solvents. Herein, we report the first living/controlled anionic ROP of GL in strong protic fluoroalcohols (FAs), which are conventionally considered incompatible with anionic polymerization. Well-defined polyglycolide (PGA, Đ < 1.15, Mn up to 55.4 kg mol-1) and various PGA-based macromolecules are obtained at room temperature for the first time. NMR titration and computational studies revealed that FAs simultaneously activate the chain end and monomer without being involved in initiation. Low-boiling-point FAs and PGA can be recycled through simple distillation and sublimation at 220 °C in vacuo, respectively, providing a promising sustainable alternative for tackling plastic pollution problems.

Ketyl Radical Anion Mediated Radical Polymerization and Anionic Ring-Opening Polymerization to Give Polymers with Low Molecular Weight Distribution.

The development of novel polymerization capable of yielding polymers with low molecular weight distribution (Đ) is essential and significant in polymer chemistry, where monofunctional initiator contains only one initiation site in these polymerizations generally. Here, ketyl radical anion species is introduced to develop a novel Ketyl Mediated Polymerization (KMP), which enables radical polymerization at carbon radical site and anionic ring-opening polymerization at oxygen anion site, respectively. Meanwhile, polymerization and corresponding organic synthesis generally couldn't be performed simultaneously in one pot. Through KMP, organic synthesis and polymerization are achieved in one pot, where small molecules (cyclopentane derivates) and polymers with low Đ are successfully prepared under mild condition simultaneously. At the initiation step, both organic synthesis and polymerization are initiated by single electron transfer reaction with ketyl radical anion formation. Cyclopentane derivates are synthesized through 3-3 coupling reaction and cyclization. Polystyrene and polycaprolactone with low Đ and a full monomer conversion are prepared by KMP via radical polymerization and anionic ring-opening polymerization, respectively. This work therefore enables both organic synthesis and two different polymerizations from same initiation system, which saves time, labour, resource and energy and expands the reaction mode and method libraries of organic chemistry and polymer chemistry.

Bio-based non-flammable foams with a circular end-of-life based on the self-foaming process

For conventional polymeric foams, over-utilization of harmful precursors and the problem with waste management are driving scientists to develop sustainable foaming methods and make polymeric foams from renewable precursors. This study developed a self-foaming system to create a lignin carbonate foam (LCF) from two non-toxic carbon storage precursors: lignin and ethylene carbonate (EC). Specifically, kraft lignin, in its isolated salt form, referred to as lignophenolate, is copolymerized with EC via the anionic ring-opening polymerization. Under the optimal condition, the gelation and solidification of the copolymers could coincide with trapping in-situ generated CO2 blowing gas from the copolymers to make the foams. Its unique composition endows the materials with comparable performances with those benchmark plastic foams (for example polyurethane foam, expanded polystyrene) considering the mechanical performances, thermal stability, shape fidelity, and non-flammability. Moreover, the carbonate linkages in LCFs render them to be reshaped or depolymerized with valuable precursors for end-of-life recycling. This study opens new avenues to fabricate polymeric foams from carbon storage precursors through a self-foaming process for applications in the construction industry.

Poly(dimethyl-diphenyl-imide)siloxane/phenolic-based double network hybrid resin coatings for ablation thermal protection

Organic-inorganic hybridization is an important way to improve ablation resistance of phenolic resin coatings (PR). However, long molecular chain silicone by copolymerization is less compatible with PR and hybrid resin will form sea-island phase, which is not favorable for further improvement of ablation resistance. Therefore, how to achieve a combination of long chain and compatibility is a major challenge. In this work, the poly(dimethyl-diphenyl-imide)siloxane (PMPI) containing imide and phenyl was synthesized by anionic ring-opening polymerization and copolymerization. Then, it was hybridized with PR to obtain PMPI/PR-based double network hybrid resin coatings with nano co-continuous phase. The oxyacetylene ablation test suggests that the resin coatings with medium phenyl content has the lowest linear ablation rate (0.055 mm/s), which is 74 % lower compared to PR (0.21 mm/s). In addition, the mechanism by which PMPI enhances ablation resistance is discussed. This work provides a promising approach to develop higher performance ablative-resistant resin coatings.

Epoxidized vinyl silicone rubber-based flexible ablative material with low linear ablation rate

Thermal stability and residual content of traditional silicone rubber at very high temperature are unsatisfactory for thermal insulations. This work used anionic ring-opening polymerization to prepare epoxidized vinyl silicone rubbers with high residual content. Their structures and properties of the rubbers were evaluated. The one with 84% vinyl and 6% epoxy group showed high thermal stability in air. Epoxidized vinyl silicone rubber/carbon fiber/aramid fiber insulators showed a linear ablation rate which met the stringent ablation performance requirements for a solid motor insulation material. In addition, the thermal degradation behavior of the epoxidized vinyl silicone rubbers was investigated in detail. This work provides a strategy to develop insulation materials for solid rocket motors.

All-polymer dynamical ionogel-like materials with benzyl-mediated ultra-strong adhesion for flexible sensor application

Ionogels, as the cutting-edge soft materials, have aroused tremendous interests in flexible electronics. However, the present ionogels are often achieved through incorporating ionic liquids (ILs) into the polymer networks, which are still suffering from the fragilities of ILs leakage and weak mechanical performances. Herein, dynamic double-network ionogel-like materials (IGMs) were fabricated in the absence of small molecule ILs. The novel IGMs could be facilely prepared via the copolymerization of functional IL monomers acting as the first network, followed by anion exchange and ring-opening polymerization of lipoic acid (LA). Especially, when benzyl-modified IL was added as the third monomer, the newly-developed poly(ionic liquid) (PIL) IGMs integrated various excellent performances, including unprecedented adhesion strength, stretchability, self-healing and absorption capabilities. Flexible sensors fabricated by the novel PIL-based IGMs could distinguish the facial expressions and body motions accurately. Moreover, PIL-based IGMs could be easily recycled and reprocessed. Thus, our finding puts forward a readily accessible feedstock for the fabrication of multifunctional all-polymer IGMs.

Novel Well-defined Polystyrene-block-Poly(lactide-co-glycolide) Block Copolymers

A facile preparation of polystyrene-block-poly(lactide-co-glycolide) PS-b-PLGA block copolymers was reported in detail. Well-defined PS-b-PLGA block copolymers were successfully obtained via living anionic polymerization and ring-opening polymerization. First, hydroxyl-terminated linear polystyrenes were prepared by living anionic polymerization. The resulting polymers were used as macroinitiators for ring-opening copolymerization of lactide and glycolide in the presence of the 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a catalyst in dichloromethane at ambient temperature. Transesterification and formation of DBU-initiated polymers were minimized by optimizing the catalyst concentration. Three block copolymers were synthesized in various molecular weights from 5000 g/mol to 33600 g/mol with low polydispersity. The formation of well-defined PS-b-PLGA block copolymers was followed by nuclear magnetic resonance spectroscopy and size-exclusion chromatography. Thermal properties of the block copolymers were investigated by thermal gravimetric analysis and differential scanning calorimetry. The morphology of the block copolymers was investigated using small-angle X-ray scattering in the bulk and via grazing incidence small-angle X-ray scattering as well as atomic force microscopy in thin film demonstrating organized nanostructures with uniform domain sizes. Overall, this manuscript describes an expanded polymer toolbox for PLGA-based polymers for next-generation lithography applications.

Dual Thermal- and Oxidation-Responsive Polymers Synthesized by a Sequential ROP-to-RAFT Procedure Inherently Temper Neuroinflammation.

This study is about multiple responsiveness in biomedical materials. This typically implies "orthogonality" (i.e., one response does not affect the other) or synergy (i.e., one increases efficacy or selectivity of the other), but an antagonist effect between responses may also occur. Here, we describe a family of very well-defined amphiphilic and micelle-forming block copolymers, which show both oxidative and temperature responses. They are produced via successive anionic ring-opening polymerization of episulfides and RAFT polymerization of dialkylacrylamides and differ only in the ratio between inert (N,N-dimethylacrylamide, DMA) and temperature-sensitive (N,N-diethylacrylamide, DEA) units. By scavenging Reactive Oxygen Species (ROS), these polymers are anti-inflammatory; through temperature responsiveness, they can macroscopically aggregate, which may allow them to form depots upon injection. The localization of the anti-inflammatory action is an example of synergy. An extensive evaluation of toxicity and anti-inflammatory effects on in vitro models, including BV2 microglia, C8D30 astrocytes and primary neurons, shows a link between capacity of aggregation and detrimental effects on viability which, albeit mild, can hinder the anti-inflammatory potential (antagonist action). Although limited in breadth (e.g., only in vitro models and only DEA as a temperature-responsive unit), this study suggests that single-responsive controls should be used to allow for a precise assessment of the (synergic or antagonist) potential of double-responsive systems.