Polyurethane foams (PUFs) are versatile materials with widespread applications, yet their synthesis involves isocyanates, which pose health and environmental risks. Non-isocyanate polyurethane foams (NIPUFs) offer a safer and more sustainable alternative through cyclic carbonate aminolysis, though achieving efficient self-blowing formulations at room temperature (RT) has proven challenging. Existing methods often require external heating and long reaction times[1,2], or hybrid formulations involving epoxides, which complicate the process[3].
This study presents a rapid, solvent-free method for producing hydroxyurethane-based NIPUFs using exo-vinylene cyclic carbonates (αCCs)[4]. The highly exothermic aminolysis of αCC[5] drives foam formation within 1–5 minutes, incorporating hydroxy-oxazolidone (cyclic hydroxy-urethane) pendant groups into the foam structure. By eliminating the need for epoxides or external heating, this method enables pristine, self-blowing NIPU foams directly from RT formulations. Furthermore, by adjusting monomer ratios, compositions, and utilizing diverse αCCs and polyamine variants, precise control over the foam's properties can be achieved. This results in flexible to semi-rigid foams with comparable pore size, density, Tg, and Td to conventional PUFs. The unique reactivity of αCC, combined with this versatility, ensures scalable and efficient foam production that can be tailored to a range of applications while maintaining sustainability. In overcoming key challenges in NIPUF development, this approach provides a practical pathway for creating customizable polyhydroxyurethane foams. As a result, it lays the foundation for the broader adoption of NIPU technology across diverse industries.

Polyisobutylene (PIB) is a rubbery polymer, which is synthesized exclusively via cationic polymerization. Due to unique properties of aforementioned polymer, including low gas permeability, chemical resistance and biocompatibility, PIB and its block copolymers are prospective materials for the usage in electronic industry and medicine¹,². In that regard, development of new facile and environmentally friendly methods for the synthesis of isobutylene block copolymers is desired. Mechanistic transformation is a promising approach in polymer synthesis that combines different polymerization modes to create novel copolymer structures. Such approach seems even more interesting in combination with visible light induced polymerization, which is a powerful synthetic tool that allows the one to conduct fast reactions with spatiotemporal control.
Herein, the simple strategy for preparation of block copolymers of isobutylene with styrene and methyl methacrylate via mechanistic transformation from cationic to photo induced radical polymerization is reported. This strategy involves the synthesis of 2-bromo-2-methylpropanoyl-terminated difunctional polyisobutylene via consecutive cationic polymerization, in situ preparation of hydroxyl-terminated polyisobutylene and its acylation by 2-bromo-2-methylpropanoyl bromide. The following Mn₂(CO)₁₀-triggered photoinduced radical polymerization utilizing this macroinitiator produces multiblock copolymer with styrene and triblock copolymer with methyl methacrylate in bulk conditions³. Thus, a novel straightforward procedure for the synthesis of PIB-based block copolymers was designed, which employed the visible light-induced polymerization. This approach may open new, simple and cost-efficient way for preparation of PIB-based block copolymers.
Acknowledgements
This work was supported by State Program for Scientific Research of Belarus “Chemical processes, reagents and technologies, bioregulators and bioorganic chemistry” (project 2.1.01.03).

The synthesis of monodisperse polystyrene nanoparticles has attracted significant attention due to their extensive applications in diverse fields¹. The emulsion polymerization process is mainly used to produce polymer nanoparticles. Despite the numerous studies on emulsion polymerization, the focus on particle size control has been limited. Moreover, most studies do not fully disclose hydrodynamic conditions, making it difficult to compare results among different research groups.
In this study, it was established that reactor geometry and stirring rate are critical factors for ensuring reproducibility in experimental results and achieving a narrow particle size distribution. The findings indicate that the diameter of the particles and the coefficient of variation are dependent on the stirring speed (Fig. 1a). The lowest value of the coefficient of variation was observed at a stirring speed of 800 rpm (Fig. 2b).

Fig.1. (a) Particle diameter and Cv vs. stirring rate dependence; (b) SEM photograph of polystyrene particles obtained at a stirring speed of 800 rpm.

In turn, the particle size can be effectively controlled by changing the concentrations of the monomer and emulsifier. It is noteworthy that changes in the initiator concentration (2.5-20 mM) exhibited a negligible influence on the particle diameter.
In summary, simple and reproducible method has been developed to obtain monodisperse polystyrene particles with diameters ranging from 110 to 590 nm (Cv<3%).

Acknowledgment: this work was carried out within the framework of the State programme for scientific research of Belarus «Chemical processes, reagents and technologies, bioregulators and bioorganic chemistry» (assignment 2.1.01.03, state registration №. 20210512).

The utilisation of epoxy resin formulations in technical fields includes composite materials, encapsulation, coatings, structural adhesives, and numerous other applications. ¹ For the curing of epoxy resins anhydrides are one of the most prevalent hardeners providing good thermal and mechanical properties. However, anhydrides bring along disadvantages for example the need of high temperatures and long reaction times. ² Additionally, anhydrides entail certain hazards, making them the focus of potential prohibition measures and regulatory provisions. An alternative could be the use of active esters for the curing of epoxides. Model reactions to determine the mechanism of this reactions were carried out by Chen et al. ³ and delivered promising results, especially regarding the modification of the polymer backbone by the type of the active ester. This is particularly interesting for manufacturing when used with easily available chemicals such as diglycidyl ether of bisphenol A (DGEBA) and active diester species. ⁴
To investigate alternative potential variations of active ester species, model reactions with phenyl glycidyl ether (PGE), catalysed with 4-dimethylaminopyridine (DMAP), were carried out. The most promising substance for this reaction was phenyl acetate. Using this system, the influence of different Lewis base catalysts was investigated as well.

Conjugated polymers have drawn considerable attention due to their remarkable electronic and optical properties, making them integral to a wide range of optoelectronic applications.1 Phenothiazine (PTZ), an electron-rich tricyclic heteroarene with nitrogen and sulfur atoms, exhibits intense luminescence, high photoconductivity, and reversible oxidation. These attributes are linked to the stability of PTZ radical cations, making PTZ derivatives ideal for donor–acceptor materials.2 Enhanced intramolecular charge transfer and photoinduced electron transfer further establish PTZ derivatives as key components in organic light-emitting diodes, field-effect transistors, chemical sensors, solar cells, and batteries.3,4
This study focuses on the synthesis of conjugated polymers incorporating 10-hexyl-phenothiazine, 10-hexyl-5-oxide-phenothiazine, and 10-hexyl-5,5-dioxide-phenothiazine. The polymers were prepared via the Suzuki-Miyaura cross-coupling reaction of their corresponding comonomers using 10 mol% Pd(PPh₃)₄ as a catalyst under basic conditions. UV-vis absorption spectra revealed that the intramolecular charge transfer effect was enhanced as the sulfur oxidation state in the PTZ core increased. Photoluminescence spectra demonstrated red-shifted fluorescence and improved quantum yields with higher oxygen content. Cyclic voltammetry indicated reversible oxidative and reductive peaks for all polymers, with sulfone and sulfoxide-containing polymers displaying superior redox stability compared to PHPT.
These results highlight the effectiveness of oxygen substitution in the PTZ core for tuning the electronic and optical properties of PTZ-based polymers. This strategy provides a valuable approach for developing advanced materials tailored for specific optoelectronic and energy-related applications.

Polylactide (PLA), the most commercially successful aliphatic polyester, is widely used in packaging materials, biomedical devices, and various consumer products. However, regular PLA has a moderate glass transition temperature (Tg = 50-60 °C),1 making it a less suitable alternative to glassy petroleum-based polymers like polystyrene (Tg = 100 °C). Aliphatic and aromatic alternating polyesters have emerged as promising alternatives to synthetic petroleum-based polymers because of their biodegradability and biocompatibility.2 These alternating polyesters can be synthesized through the ring-opening copolymerization (ROCOP) of epoxides and anhydrides. The ROCOP of cyclohexene oxide (CHO) with anhydrides, resulting in fully alternating polyesters, has attracted significant research attention due to the high Tg.3 These polyesters are widely utilized in engineering plastics, fibers, films, packaging, and biomedical applications.1,4 To date, numerous studies have focused on the ROCOP of epoxides and anhydrides using metal complexes with achiral ligands while the use of chiral metal complexes in this area remains unexplored. In this work, we synthesized both the (S) and (R) enantiomers of Al(III) compounds supported by a proline-based proligand and studied their catalytic activity towards the ROCOP of CHO with cyclic anhydrides (phthalic anhydride, succinic anhydride, and maleic anhydride). These Al(III) compounds, when combined with an ionic cocatalyst, displayed significant catalytic activity, yielding copolyesters with turnover frequencies (TOF) of up to 80 h−1, high selectivity (polyester linkages > 80%) and moderate to high Tg. The catalytic performance of the two isomers of the Al(III) complexes was compared, with the (S)-isomer showed higher activity towards the ROCOP.

Triblock copolymers encompassing a hard-soft-hard architecture are widely used as thermoplastic elastomers (TPE), a group of materials gaining increasing industrial and academic interest since its inception in the 1950s. Early prominent examples produced by living anionic polymerization employ a styrenic hard block and a soft block using butadiene (SBS) or isoprene (SIS) as monomers.¹ TPEs comprised of acrylic monomers have been explored as alternatives, due to their improved oxidation resistance and optical clarity.² This was promoted by the advent of controlled radical polymerization (CRP), offering new options for synthesis of block copolymeric architectures.

Besides more established CRP methods, reversible complexation mediated polymerization (RCMP) is a new emerging CRP.³ The polymerization is controlled by reversibly activating iodine capped polymers through an organic catalyst. The method offers a low barrier of entry, due to necessary materials being commercially widely available and relatively inoffensive towards health or the environment. Since its discovery, RCMP has demonstrated its strong capabilities in the polymerization of (meth)acrylic monomers.⁴

In this work, we investigate the synthesis of acrylic ABA block copolymers featuring a hard-soft-hard architecture using RCMP. Using a bifunctional organoiodide as an RCMP initiator, allows for the two-step synthesis of the desired triblock copolymers. Synthesis conditions for the soft block and the subsequent chain extension were explored, focusing on striking balance between attaining high molecular weights, reaching high monomer conversions and shortening reaction times. We further examined mechanical properties and microphase separation of the produced copolymers.

Nanocellulose, such as cellulose nanofibers (CNF), has attracted great interest due to its good mechanical properties, low cost, non-toxicity, low density, and thermal stability[1]. However, its high hydrophilicity remains a challenge for its application in many fields, where hydrophobic modifications of nanocellulose are necessary[2]. Therefore, we aim to prepare chemically modified cellulose nanofibers using a three-step process: 1) oxidation of cotton linter cellulose fibers with sodium hypochlorite and a catalytic amount of sodium bromide and 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO)[3]; 2) subsequent mechanical treatment to extract cellulose nanofibers; 3) solventless polymer grafting process to bond poly(butylene succinate) (PBS) oligomers on to the cellulose molecular chains under mild conditions (80-150°C). The oxidation step is functional for two main reasons: promoting the subsequent disintegration of cellulose fibers into the nanometric scale; and introducing new functional groups that can be exploited during the polymer grafting process. For the polymer grafting process, we have used succinic acid and 1,4-butanediol in equimolar amounts, while evaluating different catalysts, stabilizers, temperatures, and reaction times. The final products were characterized by ATR-FTIR, ¹H-NMR, Gel Permeation Chromatography (GPC), Scanning Electron Microscopy (SEM), and Thermal Gravimetric Analysis (TGA). The results demonstrate the success of the oxidation and the polymer grafting process, allowing this work to progress further studying the incorporation of the chemically modified nanocellulose fibers in a PBS polymer matrix to produce green polymer composites.

In recent years, ultrasound (US) irradiation has emerged as a powerful tool for polymerization utilizing acoustic cavitation triggered by US waves in a liquid medium [1, 2]. The radicals generated by the decomposition of solvent and solute molecules as a result of collapsing bubbles could be benefited to initiate the emulsion polymerization without the need for the chemical initiators. The replacement of chemical initiators with US, which promises a sustainable and environmentally friendly approach, leads to synthesis of high purity products [3]. The other superior properties of US assisted polymerization include higher monomer conversion, elimination of oxygen functioning as an inhibitor, and reduced reaction time [4]. To the best of our knowledge, this is the first comprehensive and systematic study on the parameter optimization of US assisted emulsion copolymerization of styrene (St) and 2-hydroxyethyl methacrylate (HEMA) conducted without an exogenous chemical initiator.

For this purpose, the effects of St-to-HEMA molar ratio, monomer (M)-to-water (W) ratio, and sodium dodecyl sulfate (SDS)-to-M ratio, as well as the US irradiation intensity, and the reaction temperature on polymerization yield were examined to identify the critical reaction parameters. The maximum polymerization yield (89%) was attained under the optimized conditions in terms of concentration: St/HEMA molar: 1.5, M/W ratio: 10%, and SDS/M ratio: 10%. The optimum US power and reaction temperature were determined as 34-37 W and 50oC, respectively. The copolymer structure was confirmed via FT-IR and ¹H-NMR, while the average diameter of spherical latex particles was measured as 80 nm through SEM.

Lithium-based compounds are currently the most widely used initiators for traditional polymerization reactions, especially in industrial applications. However, their use poses environmental and economic challenges due to the hazardous nature, high reactivity, and substantial costs of lithium compounds. In contrast, the electrochemical generation of initiators for living ionic polymerization offers a promising alternative. This method is safer, more cost-effective, and environmentally friendly as it avoids the need for lithium-based initiators1,2. Additionally, the electrochemical approach allows for precise control over initiator generation, potentially enhancing the polymerization efficiency and product quality.
Our studies investigate the uses of α-olefins or polycyclic aromatic hydrocarbons (PAHs) such as anthracene, naphthalene, and phenanthrene as initiators3,4. The experimental investigation involves the development of an electrochemical and spectroelectrochemical setup on a laboratory scale. The initiators are electrochemically reduced by applying a constant reduction potential by amperometric analysis, leading to the generation of a reactive intermediate. Our work can therefore provide a viable alternative to processes initiated using lithium-based compounds.

Polyimide was developed as an aerospace material in the 1960s, and its use has expanded to include microelectronics, membranes, and composites due to its excellent thermal stability, chemical resistance, and mechanical properties through the formation of charge transfer complexes(CTC). Generally, to prepare precursor polyamic acid(PAA), N-methyl-2-pyrrolidone(NMP), N,N-dimethylformamide(DMF), N,N-dimethylacetamide(DMAc) or m-cresol are used to prepare precursor polyamic acid. Polyimide is prepared by it’s cyclization reaction. Aqueous polymerization of aromatic polyamic acids(PAAS) is one of the most important challenges in polyimide research because the process is simple and environmentally friendly. Despite intensive efforts in this field, the polymerization mechanism of aqueous PAAS(W-PAAS) is still unclear, and the chemical diversity of monomers and organic bases is limited to a very narrow range. Here we report the reaction mechanism of W-PAAS polymerization in the presence of organic bases in aqueous medium. The reaction begins with the functional groups being intimately exposed to form an acid base salt between the organic base and the aromatic dianhydride. This initiation step is critical for the synthesis of PAAS and leads to the formation of stable polymer chains. Our findings reveal that polymerization occurs at the interface of the dianhydride particles in water. Further, our computational study reveals that the presence of an organic base significantly lowers the reaction energy barrier, leading to stable products with high molecular weight during the polymerization process. We believe that our eco-friendly polymerization and processing technology will not only expand the application scope, but also bring substantial environmental and economic benefits.

Towards the development of bio-based material, the design of monomers from different perspectives is needed, starting with the election of the main structure. Vanillin could be a potential starting compound as the bio-based core carrying many different functionalities including aldehyde and phenol groups. Their distribution in the aromatic ring in para positions create two separate points that allow an enormous number of transformations to a monomer.
Considering the economical aspect of bio-based materials, circularity is one of the key aspects. The incorporation of acetal groups in monomer structures was considered to provide possibility of chemical recycling under acidic conditions, increasing the chance of the recovery of the starting monomer, at the same time works as a spacer. In addition, the modification of phenol with an allyl group can allow sequential thiol-ene polymerization step.
Applying this strategy in the vanillin looking for atom efficiency, some troubles in terms of yield were found relating to the equilibrium features in the acetal formation and the acidity of the phenol group. With the goal of decipher the chemical behaviour of vanillin, a thorough study was developed studying the optimization of the synthetical path, the nature of the pKa of different substituent groups or the effect of the selected solvent in the mechanism. As result, a strategy was developed for the synthesis of highly functionalized vanillin monomers in sustainable conditions at almost quantitative yield.

With the aim of developing suitable alternatives to fossil-based commodity plastics, looking at the feedstock of bioderived monomers becomes essential to help creating a sustainable and circular plastic economy. Oxa-norbornene lactone (ONL) derivatives made from bio-based Itaconic anhydride and furfuryl alcohol have been identified as a suitable candidate for ring-opening metathesis polymerisation (ROMP).[1],[2] In our study we build on these previous findings and extend the study toward investigating the functionalisation of these ONL derivatives with different biobased esters and explore their effect on polymerisability, as well as their thermal and mechanical properties by using thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC) and tensile testing techniques.

Packaging plays a crucial role in preserving and protecting products, extending shelf life, and enhancing consumer convenience. In recent years, the demand for sustainable packaging solutions has increased significantly, driven by growing concerns about environmental pollution and the high CO₂ emissions associated with plastics production and use. Traditionally, oil-based plastics were and still are widely used in packaging due to their low cost and favorable mechanical and barrier properties. However, their negative environmental impact, both in terms of non-renewable resource exploitation and non-biodegradability, poses serious ecological challenges. As a result, there is a pressing need to reduce reliance on such materials by exploring alternatives with a lower carbon footprint. Among these, bioplastics such as poly(butylene succinate) (PBS), have emerged as promising sustainable options. PBS is a biobased and biodegradable aliphatic polyester that offers an excellent balance of thermo-mechanical properties. Yet while having these advantages, PBS is still often blended with other polymers to enhance its applicability. In this context, the current study presents a novel approach to the chemical modification of PBS. Specifically, the synthesis of block copolymers comprising PBS and another biobased polyester has been carried out following a reactive blending procedure. By varying the time during the blending process, different molecular architectures were achieved, along with tailored property modulation. Additionally, a random copolymer was also synthesized from the monomers to allow for a comparative analysis with the block copolymers. Finally, the resulting materials were processed and characterized to assess their potential as sustainable packaging solutions.

Wood has been wildly used in human history for many different applications. In the sight of biobased material economy, one could hardly ignore this bio-sourced material for its fascinating properties. However, as a chemist we look at the wood structure from a molecular and macromolecular level. Today, More and more attention is on one of the major parts of wood, namely lignin. Lignin is a complex mixture of organic macromolecules, which can provide plenty of small aromatic bio-based molecules through depolymerization. 1
Starting from acetovanillone, an aromatic molecule that can be derived from lignin and combined that with sulfur, another substance occurs wildly in nature, enabled us to craft a novel polymer. This novel polymer was created by a new synthetic pathway, consisting of two types of aromatic cycles, thiophene and methoxyphenyl. The thiophene has already been wildly studied and developed as a repeating unit of conductive polymer for its interesting electro-chemical properties. 2 In this case the methoxyphenyl group provides option for relative-stable storage of electrons via the mechanism of demethylation. Combining both structures, the new biobased polymer showed quite encouraging energy storage capacity on cyclic voltammetry. Furthermore, the internal structure provides the possibility for further chemical modifications. The work opens a new access from bio-based molecules to polymeric materials for electro-chemical applications in the green material field.

Alkyd coatings are complex mixtures derived from alkyd polymers, serving both decorative and protective purposes. These polymers are favored in formulations for their cost-effectiveness and flexibility [1]. They are considered eco-friendly resins, as most of their components come from renewable sources, though phthalic anhydride is petrochemical-based. High-solid (HS) alkyd resins with low volatile organic compound (VOC) content have been developed in response to new VOC regulations limiting their presence in decorative paints. Recently, HS alkyd resins with reduced organic solvent levels have been introduced to meet evolving EU environmental standards [2-3].
This research presents the development of environmentally friendly HS alkyd resins using soybean oil as a renewable resource to mitigate VOC emissions in industrial coatings. A two-step synthesis involves creating a soybean oil-based alkyd resin followed by copolymerization with vinyl monomers to increase solids content and enhance film properties. This approach minimizes solvent reliance, directly addressing VOC reduction. The various physic-chemical properties of alkyd resins including acid value, iodine value, density, viscosity, color and chemical resistance were studied. Thermal analysis of alkyd resins is conducted by using thermo gravimetric analysis (TGA) and thermal differential calorimeter (DSC) techniques, which reveals that these alkyd resins possess thermal stability. Resins were characterized by FT-IR spectroscopy and Gas chromatography. The resulting resin’s performance was assessed through evaluations of drying time, hardness, gloss, and adhesion. Compared to conventional alkyds, this novel resin demonstrates a significant VOC reduction while maintaining or exceeding key performance characteristics, offering a sustainable alternative for the coatings industry.

Efforts to replace petrochemical-based polymers with biomass-derived polyols have been widely pursued across various industries.[1-5] This study focuses on the synthesis of thermoplastic polyurethane (TPU) by substituting petrochemical-based polyols with bio-based polyester polyols and investigates the resulting material’s physical properties. The incorporation of bio-based polyols contributes to low-carbon technology within the context of TPU production. In this work, TPU synthesised with bio-based polyols demonstrated comparable physical properties to those formulated with petrochemical-derived polyols. The study also examined the influence of bio-polyol content on the mechanical and thermal properties of TPU. Mechanical properties, including hardness, tensile strength, and elongation, were evaluated, while thermal characteristics were analysed using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The findings indicate that TPU synthesised from bio-based polyols exhibits similar performance to conventional petrochemical-based TPU, with variations in properties depending on the bio-polyol content. This study highlights the potential of bio-based polyols in TPU synthesis, advancing the development of low-carbon technology.

In recent years lignin has been established as a promising feedstock for renewable materials due to the ever-growing need for independence from the widespread use of petrochemicals.¹ Especially biobased adhesives are of interest, as they are ubiquitous in everyday life. So far, the mussel-inspired approach of forming thiol-catechol connectivities (TCC) by reacting thiols with ortho-quinones in a Michael-type reaction² has been developed on the basis of bisphenols derived from fossil-fuels.³
In this regard we have established lignin as a feedstock for TCC adhesives by chemical demethylation of guaiacyl (G-units) to catechols followed by oxidation.⁴ The network formation via TCC ensures regeneration of the aromatic hydroxyl groups, resulting in promising shear strength in both dry and underwater applications. However, only a small fraction of lignin functional units are accessible to TCC chemistry in this manner. Therefore, improved lignin modification processes allow for the introduction of additional catechol groups into the structure, greatly increasing the number of phenolic functional groups.⁵ Oxidative activation using various hypervalent iodine reagents enables the efficient generation of quinones, which can be quantified using a novel ¹⁹F-NMR method. Crosslinking of these oxidized lignins with different liquid multithiols in a thermally induced two-component (2K) approach results in a library of bio-based lignin adhesives. The curing process of these mixtures was confirmed via Fourier-transform infrared spectroscopy and analyzed by rheological and differential scanning calorimetry methods. By varying the oxidation conditions, the resulting material properties can be greatly influenced, obtaining adhesives tailored for a variety of different applications.