Synthesis Of Block Copolymers Research Articles

Selective cross-metathesis of cellobiose derivatives with amido-functionalized olefinic structures: A model study for synthesis of cellulosic diblock copolymers

This work describes a model study for synthesis of cellulose-based block copolymers, investigating selective coupling of peracetyl β-d-cellobiose and perethyl β-d-cellobiose at their reducing-ends by olefin cross-metathesis (CM). Herein we explore suitable pairs of ω-alkenamides that permit selective, quantitative coupling by CM. Condensation reactions of hepta-O-acetyl-β-d-cellobiosylamine or hepta-O-ethyl-β-d-cellobiosylamine with acyl chlorides afforded the corresponding N-(β-d-cellobiosyl)-ω-alkenamide derivatives with an aromatic olefin or linear olefinic structures. Among the introduced olefinic structures, CM of the undec-10-enamide (Type I olefin) and the acrylamide (Type II olefin) gave the hetero-block tetramers, N-(hepta-O-ethyl-β-d-cellobiosyl)-N′-(hepta-O-acetyl-β-d-cellobiosyl)-alkene-α,ω-diamides, with >98 % selectivity. Moreover, selectivity was not influenced by the cellobiose substituents when a Type I olefin with a long alkyl tether was used. Although the amide carbonyl group could chelate the ruthenium atom and reduce CM selectivity, the results indicated that such chelation is suppressed by sterically hindered pyranose rings or the long alkyl chain between the amido group and the double bond. Based on this model study, selective end-to-end coupling of tri-O-ethyl cellulose and acetylated cellobiose was accomplished, proving the concept that this model study with cellobiose derivatives is a useful signpost for selective synthesis of polysaccharide-based block copolymers.

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.

Modular Synthesis of PEG-Dendritic Block Copolymers by Thermal Azide-Alkyne Cycloaddition with Internal Alkynes and Evaluation of their Self-Assembly for Drug Delivery Applications.

Linear-dendritic block copolymers assemble in solution due to differences in the solubility or charge properties of the blocks. The monodispersity and multivalency of the dendritic block provide unparalleled control for the design of drug delivery systems when incorporating poly(ethylene glycol) (PEG) as a linear block. An accelerated synthesis of PEG-dendritic block copolymers based on the click and green chemistry pillars is described. The tandem composed of the thermal azide-alkyne cycloaddition with internal alkynes and azide substitution is revealed as a flexible, reliable, atom-economical, and user-friendly strategy for the synthesis and functionalization of biodegradable (polyester) PEG-dendritic block copolymers. The high orthogonality of the sequence has been exploited for the preparation of heterolayered copolymers with terminal alkenes and alkynes, which are amenable for subsequent functionalization by thiol-ene and thiol-yne click reactions. Copolymers with tunable solubility and charge were so obtained for the preparation of various types of nanoassemblies with promising applications in drug delivery.

Organobase-Catalyzed Ring-Opening Copolymerization of Cyclic Anhydrides and Oxetanes: Establishment and Application in Block Copolymer Synthesis

Organobase-Catalyzed Ring-Opening Copolymerization of Cyclic Anhydrides and Oxetanes: Establishment and Application in Block Copolymer Synthesis

Design, Synthesis, and Acid-Responsive Disassembly of Shell-Sheddable Block Copolymer Labeled with Benzaldehyde Acetal Junction.

Smart nanoassemblies degradable through the cleavage of acid-labile linkages have attracted significant attention because of their biological relevance found in tumor tissues. Despite their high potential to achieve controlled/enhanced drug release, a systematic understanding of structural factors that affect their pH sensitivity remains challenging, particulary in the consruction of effective acid-degradable shell-sheddable nanoassemblies. Herein, the authors report the synthesis and acid-responsive degradation through acid-catalyzed hydrolysis of three acetal and ketal diols and identify benzaldehyde acetal (BzAA) exhibiting optimal hydrolysis profiles in targeted pH ranges to be a suitable candidate for junction acid-labile linkage. The authors explore the synthesis and aqueous micellization of well-defined poly(ethylene glycol)-based block copolymer bearing BzAA linkage covalently attached to a polymethacrylate block for the formation of colloidally-stable nanoassemblies with BzAA groups at core/corona interfaces. Promisingly, the investigation on acid-catalyzed hydrolysis and disassembly shows that the formed nanoassemblies meet the criteria for acid-degradable shell-sheddable nanoassemblies: slow degradation at tumoral pH = 6.5 and rapid disassembly at endo/lysosomal pH = 5.0, while colloidal stability at physiological pH = 7.4. This work guides the design principle of acid-degradable shell-sheddable nanoassemblies bearing BzAA at interfaces, thus offering the promise to address the PEG dilemma and improve endocytosis in tumor-targeting drug delivery.

استكشاف مفصل لتصنيع وتوصيف كوبولميرات متعددة الكتل من استر- سيلوكسان

This research paper presents a comprehensive study on the synthesis and characterization of Ester-Siloxane multi block copolymers. Two different synthesis methods, namely the one-prepolymer method and the two-prepolymer method, were employed to prepare the copolymers. The distribution of the Ester segment within the copolymers was analyzed using refractive index and ultraviolet detectors coupled with size exclusion chromatography (SEC). SEC-FTIR spectroscopy was utilized to investigate the distribution and composition of the Siloxane segment. Gel permeation chromatography (GEC) was employed to assess copolymer purity based on Siloxane content. Atomic force microscopy (AFM) was utilized to visualize the morphology of Siloxane domains in the copolymers. The results revealed the presence of well-defined Siloxane-rich domains in the form of spheres. Moreover, the occurrence of spherulitic crystal structures was observed in random copolymers with low Siloxane content and small Siloxane segment length. This research provides valuable insights into the manufacturing process, characterization, and structural aspects of multi-block ester-siloxane polymers, and contributes to the understanding of polymer design, the relationship between composition and molecular structure, and the material properties. Key words: Copolymer, -Siloxane multiblock, One-prepolymer, Two-prepolymer, Polycondensate.

Polysaccharides as a Hydrophilic Building Block of Amphiphilic Block Copolymers for the Conception of Nanocarriers.

Polysaccharides are gaining increasing attention for their relevance in the production of sustainable materials. In the domain of biomaterials, polysaccharides play an important role as hydrophilic components in the design of amphiphilic block copolymers for the development of drug delivery systems, in particular nanocarriers due to their outstanding biocompatibility, biodegradability, and structural versatility. The presence of a reducing end in polysaccharide chains allows for the synthesis of polysaccharide-based block copolymers. Compared with polysaccharide-based graft copolymers, the structure of block copolymers can be more precisely controlled. In this review, the synthesis methods of polysaccharide-based amphiphilic block copolymers are discussed in detail, taking into consideration the structural characteristics of polysaccharides. Various synthetic approaches, including reductive amination, oxime ligation, and other chain-end modification reactions, are explored. This review also focuses on the advantages of polysaccharides as hydrophilic blocks in polymeric nanocarriers. The structure and unique properties of different polysaccharides such as cellulose, hyaluronic acid, chitosan, alginate, and dextran are described along with examples of their applications as hydrophilic segments in the synthesis of amphiphilic copolymers to construct nanocarriers for sustained drug delivery.

Gem-bisphosphonic acid-based double hydrophilic block copolymers: RAFT synthesis and comparative assembly with gadolinium ions for the formation of MRI contrast agents

The synthesis of double hydrophilic block copolymers (DHBCs) with one block containing bisphosphonic acid groups was performed by aqueous RAFT polymerization with two approaches, either starting from a PEO-based macro-chain transfer agent (macro-CTA) or by chain extension of a RAFT-capped bisphosphonic acrylate homopolymer with oligo(ethylene glycol) methyl ether acrylate (OEGA). By complexation with gadolinium and europium ions, these polymers are prone to form hybrid polyionic complexes (HPICs) as evidenced by mono- and multi-angle DLS, TEM and luminescence measurements. The obtained HPICs showed better chemical stability at low pH values compared to previously reported counterparts based on carboxylic and monophosphonic acid groups (i.e., PEO-b-PAA and PEO-b-PVPA respectively). Due to their high relaxivity values, the proposed HPICs show potential as contrast agents for magnetic resonance imaging (MRI).

Single-Step Synthesis and Characterization of Non-Linear Tough and Strong Segmented Polyurethane Elastomer Consisting of Very Short Hard and Soft Segments and Hierarchical Side-Reacted Networks and Single-Step Synthesis of Hierarchical Hyper-Branched Polyurethane.

Polyurethane elastomers are among the most versatile classes of industrial polymers-typically achieved through a two-step synthesis of segmented block copolymers, comprising very long and soft segments that provide elasticity and significantly long and hard segments that provide strength. The present research focused on the design of a single-step synthesis of a new segmented polyurethane consisting of very short soft and hard segments, crosslinked by preferentially side-reacted hierarchical tertiary oligo-uret network structures, thus exhibiting significant strength, elasticity, and toughness. Despite the theoretically linear structure, both FTIR and solid-state 13C NMR spectroscopy analyses indicated the quasi-equal presence of urethane groups and tertiary oligo-uret structures in the resulting polymer, indicating a preferential consecutive side reaction mechanism. Thermal analysis indicated the significant crystallization of soft segments consisting of only four ethylene oxide units, which was, hereby, demonstrated to occur via an extended chain mechanism. Tensile mechanical properties included significant strength, elasticity, and toughness. Increasing the soft segment length led to a decreased tertiary oligo-uret secondary crosslinking efficacy. The preferential hierarchical side reaction mechanism was, hereby, further confirmed through the synthesis of a completely new type of hyper-branched polymer via diisocyanate and a mono-hydroxy-terminated reagent. The structure-property relations and reaction mechanisms demonstrated in the present research can facilitate the design of new polyurethanes of enhanced performance and processing efficacy for a variety of novel applications.

Visible Light-Regulated Ring-Opening Polymerization of Lactones by Employing Indigo as a Photoacid Catalyst.

The development of visible light-regulated polymerizations for precision synthesis of polymers has drawn considerable attention in the past years. In this study, an ancient dye, indigo, is successfully identified as a new and efficient photoacid catalyst, which could readily promote the ring-opening polymerization of lactones under visible light irradiation in a well-controlled manner, affording the desired polyester products with predictable molecular weights and narrow dispersity. The enhanced acidity of indigos by excitation is crucial to the H-bonding activation of the lactone monomers. Chain extension and block copolymer synthesis are also demonstrated with this method. This article is protected by copyright. All rights reserved.

A Powerful Strategy for Synthesizing Block Copolymers via Bimetallic Synergistic Catalysis.

Block copolymers, comprising polyether and polyolefin segments, are an important and promising category of functional materials. However, the lack of efficient strategies for the construction of polyether-b-polyolefin block copolymers have hindered the development of these materials. Herein, we propose a simple and efficient method to obtain various block copolymers through the copolymerization of epoxides and acrylates via bimetallic synergistic catalysis. The copolymerization of epoxides and acrylates proceeds in a sequence-controlled manner, where the epoxides-involved homo- or copolymerization occurs first, followed by the homopolymerization of acrylates initiated by the alkoxide species from the propagating polymer chain, thus yielding copolymers with a block structure. Notably, the high monomer compatibility of this powerful strategy provides a platform for synthesizing various polyacrylate-based block copolymers comprising polyether, polycarbonate, polythiocarbonate, polyester, and polyurethane segments, respectively.

A Powerful Strategy for Synthesizing Block Copolymers via Bimetallic Synergistic Catalysis

AbstractBlock copolymers, comprising polyether and polyolefin segments, are an important and promising category of functional materials. However, the lack of efficient strategies for the construction of polyether‐b‐polyolefin block copolymers have hindered the development of these materials. Herein, we propose a simple and efficient method to obtain various block copolymers through the copolymerization of epoxides and acrylates via bimetallic synergistic catalysis. The copolymerization of epoxides and acrylates proceeds in a sequence‐controlled manner, where the epoxides‐involved homo‐ or copolymerization occurs first, followed by the homopolymerization of acrylates initiated by the alkoxide species from the propagating polymer chain, thus yielding copolymers with a block structure. Notably, the high monomer compatibility of this powerful strategy provides a platform for synthesizing various polyacrylate‐based block copolymers comprising polyether, polycarbonate, polythiocarbonate, polyester, and polyurethane segments, respectively.

Synthesis and characterization of statistical and block copolymers of n‐hexyl isocyanate and 2‐chloroethyl isocyanate via coordination polymerization

AbstractStatistical and block copolymers of n‐hexyl isocyanate (HIC) and 2‐chloroethyl isocyanate (ClEtIC) were synthesized via cοοrdination polymerization employing the half‐titanocene complex [(η5‐C5H5)((S)‐2‐Bu‐O)TiCl2] as initiator. The complex, bearing a chiral substituent, led to optically active products, as confirmed by circular dichroism measurements. The molecular characterization of all products was carried out by NMR and IR spectroscopy and size exclusion chromatography (SEC), while their thermal stability was investigated through differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and differential thermogravimetry (DTG). The reactivity ratios of the two monomers were determined using various graphical methods, as well as the COPOINT program, according to the terminal copolymerization model. Structural parameters, such as the dyad monomer sequences and the mean sequence lengths were calculated as well. In addition, the kinetics of the thermal degradation of the statistical copolymers was studied, and the activation energies of the thermal degradation were calculated employing the Kissinger, Ozawa–Flynn–Wall (OFW), and Kissinger–Akahira–Sunose (KAS) methods. The block copolymers were synthesized by sequential addition of monomers starting from the polymerization of HIC. Well‐defined products were obtained in a controlled way as revealed by SEC, IR, and NMR measurements.

Hybrid anionic block copolymerization: From organocatalysis‐streamlined crossover to internally microphase‐separated aggregates

AbstractPolyolefin‐b‐poly(ethylene oxide) (PEO) represents the most widely investigated amphiphilic block copolymers. So far, one‐pot continuous synthesis of such hybrid block copolymers has only been fulfilled by anionic polymerization through sequential addition of vinyl monomers and ethylene oxide (EO). It still remains challenging to achieve altogether high block efficiency, high polymerization efficiency, and high molar mass for PEO. Here, we report a one‐pot hybrid block copolymerization approach to polyisoprene/polystyrene(PI/PS)‐b‐PEO, in which PI/PS are formed by sBuLi‐initiated anionic vinyl‐addition polymerization, then in situ employed as macroinitiators for the anionic ring‐opening polymerization (ROP) of EO aided by an organic Lewis pair. The cooperative (dual‐ion‐complexing) catalytic effect of organobase and triethylborane is proven, for the first time, effective for lithium alkoxide initiator system, allowing to achieve at room temperature high ROP activity (complete EO conversion and PEO of 3–64 kg/mol reached in 1–6 h), narrow molar mass distribution, controlled block lengths and composition. Density functional theory calculation shows that phosphazene bases are particularly effective, compared with N‐heterocyclic bases, for complexing with Li+ and enhancing the nucleophilicity of oxyanion. The rate of ROP is also affected by Li+‐induced aggregation of the chain‐end ion pairs, which though can be offset by adequate catalyst loadings. The versatility of this approach is further demonstrated in the one‐pot synthesis of tri‐/tetrablock ter‐/quaterpolymers constituted by PI, PS, PEO, and poly(propylene oxide). Of great interest, PS‐b‐PI‐b‐PEO triblock terpolymer with a specific composition is found to form internally microphase‐separated micellar aggregates when dispersed in water.

Click synthesis of an adhesive block copolymer with poly(3-hexylthiophene) and poly(vinyl catechol) segments

Click synthesis of an adhesive block copolymer with poly(3-hexylthiophene) and poly(vinyl catechol) segments

Toward the production of block copolymers in microbial cells: achievements and perspectives.

The microbial production of polyhydroxyalkanoate (PHA) block copolymers has attracted research interests because they can be expected to exhibit excellent physical properties. Although post-polymerization conjugation and/or extension have been used for PHA block copolymer synthesis, the discovery of the first sequence-regulating PHA synthase, PhaCAR, enabled the direct synthesis of PHA-PHA type block copolymers in microbial cells. PhaCAR spontaneously synthesizes block copolymers from a mixture of substrates. To date, Escherichia coli and Ralstonia eutropha have been used as host strains, and therefore, sequence regulation is not a host-specific phenomenon. The monomer sequence greatly influences the physical properties of the polymer. For example, a random copolymer of 3-hydroxybutyrate and 2-hydroxybutyrate deforms plastically, while a block copolymer of approximately the same composition exhibits elastic deformation. The structure of the PHA block copolymer can be expanded by in vitro evolution of the sequence-regulating PHA synthase. An engineered variant of PhaCAR can synthesize poly(D-lactate) as a block copolymer component, which allows for greater flexibility in the molecular design of block copolymers. Therefore, creating sequence-regulating PHA synthases with a further broadened substrate range will expand the variety of properties of PHA materials. This review summarizes and discusses the sequence-regulating PHA synthase, analytical methods for verifying block sequence, properties of block copolymers, and mechanisms of sequence regulation. KEY POINTS: • Spontaneous monomer sequence regulation generates block copolymers • Poly(D-lactate) segment can be synthesized using a block copolymerization system • Block copolymers exhibit characteristic properties.

Retrospective Analysis of Polyethylene Oxide and Polypropylene Oxide Block Copolymers Production and Industrial Applications (Review)

Introduction. Nowadays block copolymers of PEO and PPO (poloxamers, pluronics, proxanols) are among the most popular polymers in the pharmaceutical and biotechnological industries. They can be applied as effective nonionic surfactants, biological membrane stabilizers, elements of targeted delivery systems, solubilizers, as well as excipients in the technology of traditional dosage forms – gelling agents, lubricants, etc. For the past fifty years, the world's largest manufacturer of poloxamers has been the German chemical concern BASF. However, today in the Russian Federation there is a risk of defects, which defines the relevance of import substitution of this excipient.Text. The purpose of this review is to highlight the experience of production and implementation of PEO and PPO block copolymers into novel Russian scientists’ developments, comparing them with the experience of foreign research groups, which is necessary to assess the potential for import substitution. PEO and PPO block copolymers have been known in the Soviet Union since the late 60s as far as they are mentioned in textbooks of 1964 and 1973. Domestic block copolymers of PEO and PPO have been used in the oil refining industry, as well as in some branches of light industry and in the decontamination of radioactive waste. The unique domestic synthesis of PEO and PPO block copolymers was established in 1978 on the basis of the "Orgsintez" factory. Soviet poloxamers were produced under the brand name "proxanol" in a wide range of ratios of EO and PO units and molecular weights. It should be noted that today in the Russian Federation, industrial batches of the solubilizer Emuxol 268, which is close in its properties to the well-known poloxamer 188, are still produced, and block copolymers with other ratios of EO and PO units are synthesized to order.Conclusion. According to the retrospective analysis, the modern Russian industry has enough experience and resources to establish the synthesis of PEO and PPO block copolymers necessary to produce drugs and to develop innovative delivery systems and drugs. Based on the materials of the systematic review, the most complete register of known brands of PEO and PPO block copolymers synthesized over the past 50 years in our country and in the world was compiled for the first time, with a detailed description of their physicochemical properties.

Synthesis of Amphiphilic Block Copolymer and Its Application in Pigment-Based Ink.

Amphiphilic block copolymers-based aqueous color inks show great potential in the field of visual communication design. However, the conventional step-by-step chemistry employed to synthesize the amphiphilic block copolymers is intricate, with low yield and high economic and environmental costs. In this work, we present a novel method for preparing an amphiphilic AB di-block copolymer of PCL-b-PAA by employing a combined polymerization strategy that involves both cationic ring-opening polymerization (ROP) of the ε-caprolactone monomer and the reversible addition-fragmentation chain-transfer (RAFT) polymerization on the acrylic acid monomer simultaneously. The corresponding polycaprolactone (PCL) and polyacrylic acid (PAA) serve as the hydrophobic and hydrophilic units, respectively. The effectiveness of the amphiphilic AB di-block copolymer as the polymeric pigment dispersant for water-based color inks is evaluated. The amphiphilic AB di-block copolymer of PCL-b-PAA exhibits a molecular weight of 1400 g mol-1, which is consistent with the theoretical value and suitable for polymeric dispersant application. The high surface excess (Γmax) of the PCL-b-PAA in water indicates a densely packed molecular morphology at the water/air interface. Additionally, micelles can be stably formed in the aqueous PCL-b-PAA solution at very low concentrations by demonstrating a low CMC value of 10-4 wt% and a micelle dimension of approximately 30 nm. The model ink dispersion is prepared using organic dyes (Disperse Yellow 232) and the amphiphilic block copolymer of PCL-b-PAA. The dispersion demonstrates near-Newtonian behavior, which is highly favorable for the application as inkjet ink. Furthermore, the ink dispersion displays a low viscosity, making it particularly suitable for visual communication design and printing purposes. Moreover, the ink dispersion demonstrates an unimodal distribution of the particle size, with an average diameter of approximately 500 nm. It retains exceptional stability of dispersion and even conducts a thermal aging treatment at 60 °C for 5 days. This work presents a facile and efficient synthetic strategy and molecular design of AB di-block copolymer-based dispersants for dye dispersions.

Acid-triggered radical polymerization of vinyl monomers

Reversible addition–fragmentation chain-transfer (RAFT) polymerization is one of the most versatile and robust controlled radical polymerization methods owing to its broad material scope and high tolerance to various functionalities and impurities. However, to operate RAFT polymerization, a constant supply of radicals is required, typically via exogenous thermal radical initiators that are not only challenging to transport and store, but also primarily responsible for termination and end-group heterogeneity. Here we present an acid-triggered RAFT polymerization that operates in the dark and without any conventional radical initiator. Abundant acids (for example, sulfuric acid) are shown to have a dual role initiating and accelerating the polymerization. The polymers prepared have low dispersity and high end-group fidelity. The method is compatible with a wide range of vinyl monomers and solvents, and can be applied to the synthesis of well-controlled high molecular weight block copolymers, as well as to free radical polymerization.

Block copolymer synthesis in ionic liquid via polymerisation-induced self-assembly: a convenient route to gel electrolytes.

We report for the first time a reversible addition-fragmentation chain transfer polymerisation-induced self-assembly (RAFT-PISA) formulation in ionic liquid (IL) that yields worm gels. A series of poly(2-hydroxyethyl methacrylate)-b-poly(benzyl methacrylate) (PHEMA-b-PBzMA) block copolymer nanoparticles were synthesised via RAFT dispersion polymerisation of benzyl methacrylate in the hydrophilic IL 1-ethyl-3-methyl imidazolium dicyanamide, [EMIM][DCA]. This RAFT-PISA formulation can be controlled to afford spherical, worm-like and vesicular nano-objects, with free-standing gels being obtained over a broad range of PBzMA core-forming degrees of polymerisation (DPs). High monomer conversions (≥96%) were obtained within 2 hours for all PISA syntheses as determined by 1H NMR spectroscopy, and good control over molar mass was confirmed by gel permeation chromatography (GPC). Nanoparticle morphologies were identified using small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), and further detailed characterisation was conducted to monitor rheological, electrochemical and thermal characteristics of the nanoparticle dispersions to assess their potential in future electronic applications. Most importantly, this new PISA formulation in IL facilitates the in situ formation of worm ionogel electrolyte materials at copolymer concentrations >4% w/w via efficient and convenient synthesis routes without the need for organic co-solvents or post-polymerisation processing/purification. Moreover, we demonstrate that the worm ionogels developed in this work exhibit comparable electrochemical properties and thermal stability to that of the IL alone, showcasing their potential as gel electrolytes.