This work presents a systematic investigation into the solvent-free aminolysis of industrially relevant cyclic carbonates-specifically ethylene carbonate (EC) and propylene carbonate (PC)-with a series of structurally diverse diamines. The primary objective is to establish practical structure-reactivity relationships that, enable the rational synthesis of hydroxy-terminated urethane diols. These diols are subsequently evaluated as building blocks for the preparation of non-isocyanate urethane (meth)acrylates (NIU(M)As). By employing diamines in place of toxic diisocyanates, this synthetic strategy not only circumvents the use of conventional isocyanate chemistry, but also significantly expands the accessible structural diversity of urethane (meth)acrylates, including architectures that are difficult or impossible to obtain through traditional routes. The aminolysis reaction was monitored in real time by ATR-FTIR spectroscopy, tracking the consumption of the carbonate C & boxH;O bond, and was complemented by residual amine titration. The structures of the resulting urethane diols and their NIU(MA) derivatives were confirmed by NMR spectroscopy. The study reveals clear, structure-dependent reactivity trends: aliphatic diamines undergo rapid ring-opening under mild conditions (40 degrees-75 degrees C), whereas aromatic diamines show no measurable conversion, even at elevated temperatures. This contrast underscores the dominant role of amine nucleophilicity in determining reaction kinetics. Furthermore, aminolysis of the unsymmetrical PC yields mixtures of regio isomeric urethane diols containing primary and secondary hydroxyl groups depending on the structure of amine, a direct consequence of competing ring-opening pathways. To demonstrate the practical utility of this approach, a representative urethane diol was successfully converted into a NIU(M)A derivative. The product was characterized by NMR, IR, GPC, and photo-DSC, confirming the viability of this synthetic route for producing UV-curable formulations. These findings provide critical insights into the interplay between cyclic carbonate structure, amine reactivity, and product selectivity. This work thereby supports the rational design and development of advanced, non-isocyanate-based urethane materials for a range of potential applications.

Low-temperature plasma treatment is demonstrated as an effective strategy to enhance the gas separation performance of a vinyl-addition polymer synthesized from the industrially available monomer 5-ethylidene-2-norbornene (APENB). The plasma modification introduces controlled surface and near-surface functionalities without compromising the bulk integrity of the polymer matrix. Structural and physicochemical analyses (XPS, FTIR, AFM) confirmed the incorporation of polar functional groups into the surface layer, resulting in a significantly improved permeability-selectivity balance. A systematic investigation of air plasma treatment conditions revealed the optimal parameters for enhancing gas transport performance. A 30-s plasma exposure was found to be optimal, yielding a more than twofold increase in O2/N2 selectivity and over a 20-fold enhancement in He/ CH4 and H2/CH4 selectivity. Aging studies over a one-month period showed that the improved transport properties remained stable, with the H2/CH4 performance of treated polymer exceeding the 2015 Robeson upper bound. This work highlights the potential of plasma-based surface engineering to unlock advanced transport properties in commercially viable membrane materials for industrial gas separation.

Block copolymers (BCPs) have emerged as a fascinating tool within the realm of gas separation membranes, primarily for their remarkable ability to self-assemble into well-defined microstructures. This unique characteristic enables them to achieve an excellent balance between gas separation performance and mechanical strength. This review delves deeply into the methods of synthesizing BCPs and their self-assembly mechanisms in solution, alongside recent advancements in their application to gas separation membranes. Emphasis is placed on summarizing and discussing how neat BCP membranes and hybrid membranes optimize the CO2 separation performance through the transition of their microstructures. Lastly, the review outlines the remaining obstacles and potential advancements in the development of BCP-based membranes for gas separation and CO2 capture applications.

A two-step method for the synthesis of Ge-containing polynorbornenes with various environment of heteroatoms in the substituents was developed. The approach is based on a catalytic hydrogermylation reaction between 2,5norbornadiene and monohydrogermanes (HGeR3, where R = alkyl or aryl) followed by the polymerization via ROMP or VAP schemes. The effective catalysts of hydrogermylation reaction leading to a target product (Gesubstituted norbornene) were found: in the case of GeEt3 substituted norbornenes, it is (acac)Rh(CO)2; in the case of triarylgermyl substituted norbornenes, it is Pd-based system with (R)-MOP ligand. The polymerization of Gesubstituted norbornenes results in amorphous glassy soluble polymers capable to form free-standing films. Gesubstituted polynorbornenes display moderate gas permeability, high selectivity for CO2/N2 separation (up to 36 for pure gases and 15 for mixed gases), and solubility-controlled permeation of C1-C4 hydrocarbons. Unexpectedly, in comparison to SiEt3 substituted related polymers, GeEt3 substituted ones are characterized by simultaneously higher CO2 permeability and selectivity for CO2-containing pairs of gases. This is the first demonstration that tuning the nature of organoelement moieties in side chains can lead to the improvement of gas permeability and separation selectivity together at the replacement of Si atoms with Ge atoms in substituents. The parameters of a vinyl-addition polynorbornene with GeEt3 substituents are near 2008 upper bound in Robeson's plot.

High-molecular-weight metathesis polynorbornene containing triethylene glycol fragments linked to the main chain through a carboxyl group has been synthesized for the first time. Gas-transport parameters of the polynorbornene were investigated for the extended set of gases: H2, He, Ar, N2, O2, CO2, CH4, C2H2, C2H4, C2H6, C3H6, C3H8, CHF3, CH2F2, CF2Cl2, CHF2Cl, and NH3. The gas-transport properties of the polymer are stable during six months. The increased permeability coefficients of CO2, ethylene, acetylene, propylene, freons and ammonia are determined by their high solubility coefficients. The point for the polymer synthesized in the work is located higher than the 2008 Robeson upper bound in the selectivity-permeability diagram for CO2/N2 gas pair, which arises from the specific interaction of CO2 with the polymer. The analysis of specific interactions was carried out using correlation ratios of diffusion coefficients with the effective cross-section of gas molecules and solubility coefficients with Abraham parameters. Nonspecific and specific solubility and diffusion coefficients and their ratios for CO2, acetylene, ethylene, propylene, freons and ammonia were obtained. Based on the data obtained, the Abraham coefficients for the synthesized polymer (the "fingerprint" of the polymer) are calculated, which make it possible to estimate the solubility coefficient of gas or vapor for which the Abraham parameters are tabulated. The diffusion coefficients of gas or vapor for which the values of the effective cross-section of the molecule are tabulated can be estimated using the Teplyakov-Meares model, and, consequently, the permeability coefficient can be calculated. The proposed model has significant potential, however, given that the values obtained are calculated, the predicted gas transport parameters of the polymer are estimates.

A series of cationic palladium complexes of the composition [(NHC)Pd(allyl)(PR3)]+BARF-containing N-heterocyclic carbene (NHC) and phosphine ligands of different nature, and a weakly coordinating borate anion were synthesized. Such Pd complexes were for the first time investigated as single-component catalysts for vinyl-addition polymerization of norbornene and its functionalized derivatives. The complexes exhibit high catalytic activity without the need for co-catalysts (to 7 & sdot;106 gpolymer/molPd h). Polymers synthesized over these Pd complexes in question are characterized by unimodal GPC curves, narrow molecular weight distributions, and linear dependence of the molecular weight on the monomer conversion, which suggests the occurrence of controlled polymerization. It was demonstrated that both the structure of NHC and the nature of phosphine ligand have strong effect on catalytic activity and initiation efficiency. A correlation between Pd-P bond length and the behavior of the complex in the polymerization reaction was revealed, viz.: the shorter Pd-P bond the lower the lability of the phosphine, the initiation efficiency, and the higher the molecular weights of the resulting polymers. As a result, polymerization on the title complexes allows one to obtain polymers with much higher molecular weights compared to polymers synthesized using similar (NHC)Pd systems with other labile ligands. Besides, the synthesized complexes demonstrate high thermal stability and retain their catalytic activity at elevated temperatures. Generally, the presence of the NHC and phosphine ligands in palladium coordination sphere provides a unique balance between the activity, stability, and possibility to obtain high-molecular-weight products. This makes the complexes in hand promising catalysts for targeted synthesis of functional polymeric materials.

Vinyl-addition polymers were produced from norbornene-type monomers based on renewable feedstocks and their gas transport properties were assessed. The monomers containing (3-pinene and alpha-alanine moieties were synthesized and subjected to the polymerization on single component Pd catalysts with N-heterocyclic carbene ligands, affording high-molecular weight products (Mn <= 4.9 & sdot;105) with narrow molecular weight distributions (<= 1.2) in good to high yields. The prepared vinyl-addition polynorbornenes are glassy and amorphous polymers, possessing good film-forming properties. The study of their gas separation efficiency showed that these polymers have high CO2/gas selectivities and do not obey the trade-off between gas permeability and selectivity. For example, the polymer with alpha-alanine moieties in the side chains exhibited CO2 permeability of 190 Barrer and CO2/N2 selectivity of 44, noticeably outperforming the separation performance of industrial membrane polymers (cellulose acetate, polysulfone, and Matrimid (R)) and the related polynorbornene with pinanyl groups (P(CO2) = 39 Barrer and alpha(CO2/N2) = 31). This clearly indicates that the incorporation of an additional polar functionality (an ester motif) in the side chains can have a synergistic effect, simultaneously improving both CO2 permeability and CO2/gas selectivity. The obtained results are considered along with DSC, DMA and TGA analysis, WAXD study and free volume distribution in these polymers.

The incorporation of polycyclic moieties and methyl groups into the structure of rigid-chain glassy polymers are two known approaches to improve their gas transport properties. In this study, the combination of these approaches is reported for polynorbornenes. More specifically, the gas transport characteristics of glassy microporous polynorbornenes containing methylated 9,10-dihydroanthracene pendant substituents were systematically studied. These membranes exhibit a combination of relatively high permeability (maximum CO2 permeability is 1600 Barrer) and good separation parameters (alpha[CO2/N2] up to 41, alpha[O2/N2] up to 4.8) and noticeably better gas separation characteristics compared to analogous polymers without Me-groups. The results obtained indicate that methyl groups positively influence the gas separation performance of glassy polynorbornenes when they are rigidly bonded to the main polymer chains, even through polycyclic moieties. This effect appears to strengthen as the number of methyl groups per substituent increases.

Herein for the first time comprehensive analysis of commercial phosphine oxide-based photoinitiators was done for vat photopolymerization 3D printing resins. Resin accuracy, reactivity and cytotoxicity have been evaluated for the studied photoinitiators in different UV curable systems. Different methods for the accuracy assessment (pin hole, Dp) were used and it was shown that phenylbis(2,4,6-trimethylbezoyl)phosphine oxide (BAPO) possessed the highest x–y–z accuracy. It was shown that the increase of photoinitiator content in all cases resulted in the increase of accuracy and reactivity. The higher absorption value of a photoinitiator at a wavelength resulted in a higher reactivity and higher accuracy of corresponding VPP resin. It has been also estimated that for all studied samples, HSF cell viability was higher than 90

A simple and efficient two-step method for the synthesis of organosilicon substituted polynorbornenes containing four Si-O-C moieties at each Si atom was proposed. The method is based on a transesterification reaction between tetra(alkoxy)silanes and 5-norbornene-2-methanol followed by Ru- or Pd-catalyzed polymerization (ringopening metathesis or vinyl-addition polymerization, respectively). Using this method, we synthesized two series of high-molecular-weight polymers. Finally, the gas separation performance of the synthesized polymers was studied systematically. The polymers exhibited moderate gas permeability and perspective gas separation selectivities: P(CO2) up to 840 Barrer, CO2/N2 separation selectivity up to 56, and n-butane/methane separation selectivity up to 17. Overall, the synthesized polymers showed a better combination of gas separation performance and selectivity compared to analogous polymers with trialkylsiloxy groups. The analysis of the gas diffusion and solubility coefficients made the effect of Si-O-C moieties more understandable. More specifically, it was confirmed that the high CO2/gas separation selectivity of polynorbornenes containing these moieties in side chains is due to the specific dipole-quadrupole interaction between CO2 molecules and Si-O-C moieties. The influence of the length of alkyl tail fragments on the CO2 separation performance turned out to be sensitive to the mobility of the main chains, but the general trend was the increase in CO2/gas selectivity with the reduction in the size of alkyl tails. The largest contribution of the specific interaction to CO2 solubility and the highest CO2/N2 separation selectivity was achieved in the case of the metathesis polymer containing methyl tail fragments in substituents. The gas separation properties of the synthesized new polymers are considered together with the data of the wide-angle XRD study, TGA, and DSC analysis, as well as the free volume content.

Herein, a systematic investigation of the effects of light intensity on double bond conversion in resins for vat photopolymerization is conducted and their mechanical properties are evaluated. For this aim, a urethane acrylate resin is synthesized and the structure is confirmed by means of NMR, IR, atmospheric pressure photoionization (APPI) and GPC. Photopolymer compositions based on it are studied. It is shown that an increase in light intensity resulted in a decrease in the double bond conversion for the transparent composition. An increase in temperature during photopolymerization led to an initial growth of double bond conversion, followed by a subsequent decrease. These findings are validated through bending and tensile strength analyses.

We propose a new route to liquid branched hydrocarbon oligomers that can be of interest as potential synthetic oil base stocks. The core of the approach is the ring-opening metathesis polymerization of a norbornene derivative. Oligomerization of 5-n-butyl-2-norbornene in the presence of low loadings of the second-generation Grubbs catalyst and 1-hexene used as a chain transfer agent afforded oligomeric products with a degree of oligomerization in the range of 1 to 7. The metathesis oligomers were hydrogenated using a one-pot technique over the residual ring-opening metathesis polymerization (ROMP) catalyst. After oligomerization and modification, the product yields exceeded 99% and 94%, respectively. Both series of synthesized oligomers are characterized by low glass transition temperatures, which lie in the range from -45 to -125 degrees C, and depend primarily on the degree of polymerization and on the nature of the main chains. Detailed studies of the rheological properties showed the glass-forming behavior of the synthesized oligomers, allowing for tuning their viscosity in a wide range at any desired temperature, e.g., from 1.4105 to 4.110-2 Pas at -40 degrees C. The viscosity characteristics of the systems in question are governed by the degree of oligomerization and by the structure of the main chains. Tribological tests revealed a low friction coefficient of steel surfaces when using norbornene oligomers as lubricating oils and a significant wear reduction in comparison with commercial mineral and polyalphaolefin base oils. These results offer prospects for the targeted synthesis of norbornene oligomers with desired low-temperature parameters and remarkable antiwear performance.

Addition polymerization of three norbornene-type monomers derived from various diamines and cis-5-norbornene-exo-2,3-dicarboxylic acid anhydride in the presence of Pd complexes with an N-heterocyclic carbene ligand was studied. The polymerization conditions for these bifunctional polymers containing imide fragments were optimized, which made it possible to produce the target polymers in yields of up to 75

Thermally rearranged (TR) polymers are unique high-performance materials with rigid aromatic rings like benzoxazoles and benzimidazoles, that are produced/transformed by heat treatment at higher temperature. TR polymers possess excellent gas separation properties, corrosion resistance and thermal stability for promising industrial applications. This critical review highlights recent advances in TR polymer based membranes for gas separation mostly in the last five years. From structural design methods to high-performance gas separation applications, we have summarized the monomer architecture design, copolymerization, cross-linking, blending, and other strategies used to enhance the comprehensive properties (such as gas separation properties and mechanical properties) of TR polymer based membranes. Finally, future directions for TR polymeric membranes are proposed for energetic-efficient gas separations mainly targeting at carbon capture and hydrogen purification.

The development of polymers with high separation characteristics for the efficient removal of carbon dioxide from bio-/natural gases is the key to reducing the environmental impact of CO2. In this work, preparation and gas-separation properties of novel vinyl-addition polynorbornenes containing oxirane-moieties at spiro centers, which combine high CO2-permeability with remarkable selectivities for separation of CO2 from its mixtures with nitrogen and methane are published. Gas permeability data of the epoxidized polymer based on 5-ethylidene-2-norbornene exceed the Robeson upper bound of 2019 for the CO2/N-2 system (CO2 permeability is 1000 Barrer, alpha(CO2/N-2) = 67)). Separation experiments with mixtures of gases confirm the high separation performance of this polymer. In particular, the data for CO2/CH4 separation are above or close to the upper bound of 2018 for mixed gases. A similar effect of introducing oxirane moieties into spiro centers is also shown for another vinyl-addition polymer derived from 5-isopropylidene-2-norbornene and is not observed for a related polymer bearing oxirane moieties at the ends of side chains. A simple synthesis of the epoxidized polymer from available 5-ethylidene-2-norbornene, combined with high CO2-permeability and selectivities, may open a window for industrial applications of this polymer in important membrane processes, in particular, for natural/biogas upgrading.

Cellulose acetate, some polyimides and polysulfones are mainly used in commercial membranes for gas separation processes. Although these polymers meet the desired combination of properties, the design of novel polymers possessing improved permeability and/or separation selectivity of gases could lead to enhanced gas separation efficiency and minimized energy costs. Here, we report gas permeability data of two isomeric vinyl-addition polymers derived from available ester-functionalized norbornenes that exhibit remarkable ideal and mixed gas selectivity as well as permeability for industrially important pairs of gases (CO2 with N2 and CH4). In particular, polynorbornene bearing acetoxy side groups (AcPNB) demonstrated carbon dioxide permeability of 270 Barrer and selectivity of CO2/N2 separation above 20, superposing to that of cellulose acetate (CA) in CO2 separation performance. The polymer containing methoxycarbonyl groups (McPNB), which is an isomer of AcPNB, showed even higher separation performance for CO2-containing gas mixtures. Carbon dioxide permeability and selectivity of CO2/N2 for McPNB exceeded 350 Barrer and 50, respectively. The data on CO2/N2 separation for McPNB are on the upper bound of Robeson plot of 2008 year. Mixed gas experiments performed for binary mixtures of CO2 with N2 and CH4 confirmed promising gas-separation parameters of the studied polymer, displaying attractive CO2/gas selectivity and CO2 permeability. Therefore, considering the simple and cheap syntheses of these polymers and the CO2 separation performance, they can be considered as promising candidates as selective layers for membrane gas separation processes.

Metathesis homo- and copolymerization of bifunctional monomers bearing two norbornene moieties was studied. The monomers were synthesized from cis-5-norbornene-exo-2,3-dicarboxylic anhydride and various diamines (hexamethylenediamine, decamethylenediamine, 1R,3S-isophoronediamine). The metathesis homopolymerization of these bis(nadimides) in the presence of the second-generation Grubbs catalyst afforded glassy cross-linked polymers in more than 90% yields. The metathesis copolymerization of the bis(nadimides) and a monofunctional norbornene derivative containing the β-pinene fragment also resulted in insoluble cross-linked polymers in nearly quantitative yields. The structures and purity of the synthesized polymers were confirmed via IR spectroscopy and CP/MAS NMR spectroscopy. Conditions for the fabrication of mechanically strong solution-cast thin films based on copolymers synthesized from the comonomers mentioned above were determined by varying the content of the cross-linking agent. It was shown that the films made in this way are stable in a range of organic solvents and could be useful as semipermeable or membrane materials for use in liquid organic media. The permeability of the polymer films in question to 1-phenylethanol and mandelic acid was studied. The results obtained are discussed along with the data from the DSC, TGA, and powder X-ray diffraction studies of the properties of the synthesized metathesis homo- and copolymers.

Spiro-Epoxy Moieties Vinyl-addition polynorbornenes with spiro epoxy moieties show exceptional separation characteristics for industrial important pairs of gases, namely, CO2/CH4 and CO2/N2. In article number 2405461, Maxim V. Bermeshev and co-workers show that the discovered effect of spiro epoxy moieties on CO2 separation performance can become a new powerful tool for the targeted development of polymers, possessing enhanced permeability of CO2 and CO2/gas selectivities.

A set of new norbornene-type monomers containing linear and branched substituents with three C-O-C fragments was synthesized in good yields from commercially available glycerol and diethylene glycol monomethyl ether. Vinyl-addition polymerization of the synthesized monomers was systematically studied, and highly active Pd-catalysts that made it possible to reach quantitative conversions of the monomers were suggested for their polymerization. As a result, robust thin membranes were successfully prepared directly from the polymerization mixtures in the air. Gas separation performance for a wide range of gases was evaluated for the synthesized polymers, and new valuable structure-property relationships were found. More specifically, these membranes display the facilitated transport of CO2 and solubility-controlled hydrocarbon separation selectivity. The increase in the amount of C-O-C fragments in side chains enhances these effects, but only in the case of the linear structure of the substituents. If the structure of side chains becomes branched, the gas permeability is reduced, the facilitated transport of CO2 is minimized, and the polymer becomes more susceptible to plasticization by butane. The facilitated transport of CO2 is due to the specific dipole-quadrupole interaction between CO2 molecules and polymer matrix. For the studied polymers, the contribution of this specific interaction to the solubility of CO2 achieves 64 %. The significant influence of alkyl tails in side chains on gas transport properties was also observed. To achieve better gas separation performance, it is desirable to incorporate short and rigid alkyl tails. Thus, among substituents containing ether moieties, linear oligoethylene glycols with methyl tails seem to be the most promising side-chain substituents for the macromolecular design of CO2-selective polymeric membrane materials. The results obtained were considered along with NMR, TGA, DSC, DMA, and WAXD data.

Sorption of carbon dioxide, methane, and hydrogen in additive poly(5-norbornyl-2-norbornene) was studied at pressures in the interval 0–10 bar and temperatures in the interval 10–60°C. The isotherms obtained were described by the double sorption model including both Langmuir and Henry sorption models. The double sorption model parameters and the gas solFigubility coefficients in the polymer at different pressures and at infinite dilutions were determined. The solubility selectivity values were calculated from the data obtained. The highest solubility selectivity for the CO2/CH4 gas pair is reached at 20°С. Owing to high values of this selectivity, additive poly(5-norbornyl-2-norbornene) can be considered as a candidate membrane material for the separation of gas mixtures containing CO2.