Synthesis Of Polymers Research Articles

A Self‐assembly of New Cobalt Coordinating Polymer Based on Fluorinated Secondary Building Unit and Pyrazine

The direct two‐step synthesis of new coordination polymer [Co2(pyz)(tfa)2(dmf)6(H2O)][Co3(μ3‐F)(tfa)6(Htfa)2(pyz)(dmf)]2·2dmf, (where pyz = pyrazine, Htfa = trifluoroacetic acid, dmf = dimethyl formamide) containing the fluoro‐centered secondary building block [Co3(μ3‐F)(tfa)6], is reported. The substance characterization using single‐crystal XRD, powder XRD, IR‐spectroscopy and thermogravimetry was performed. SCXRD data revealed the presence of cationic and anionic subsystems, both containing cobalt(II) ions and pyrazine bridging ligands. The magnetic proper‐ties of the compound were collected and discussed. Temperature dependence of magnetic susceptibility shows Curie – Weiss like behavior at all studied temperatures.

Degradable π-Conjugated Polymers.

The integration of next-generation electronics into society is rapidly reshaping our daily interactions and lifestyles, revolutionizing communication and engagement with the world. Future electronics promise stimuli-responsive features and enhanced biocompatibility, such as skin-like health monitors and sensors embedded in food packaging, transforming healthcare and reducing food waste. Imparting degradability may reduce the adverse environmental impact of next-generation electronics and lead to opportunities for environmental and health monitoring. While advancements have been made in producing degradable materials for encapsulants, substrates, and dielectrics, the availability of degradable conducting and semiconducting materials remains restricted. π-Conjugated polymers are promising candidates for the development of degradable conductors or semiconductors due to the ability to tune their stimuli-responsiveness, biocompatibility, and mechanical durability. This perspective highlights three design considerations: the selection of π-conjugated monomers, synthetic coupling strategies, and degradation of π-conjugated polymers, for generating π-conjugated materials for degradable electronics. We describe the current challenges with monomeric design and present options to circumvent these issues by highlighting biobased π-conjugated compounds with known degradation pathways and stable monomers that allow for chemically recyclable polymers. Next, we present coupling strategies that are compatible for the synthesis of degradable π-conjugated polymers, including direct arylation polymerization and enzymatic polymerization. Lastly, we discuss various modes of depolymerization and characterization techniques to enhance our comprehension of potential degradation byproducts formed during polymer cleavage. Our perspective considers these three design parameters in parallel rather than independently while having a targeted application in mind to accelerate the discovery of next-generation high-performance π-conjugated polymers for degradable organic electronics.

Synthesis, Characterization and Application of New Polymers Imprinted with Zinc (II) Ions

In this work, molecularly imprinted polymers with zinc imprints and their comparison polymers without imprints were synthesized. A comparative characterization of the physical parameters of the synthesized zinc-imprinted (ZnIP) and non-imprinted (NIP) polymers was carried out using the methods of elemental analysis, conductometry, scanning electron microscopy, and IR-Fourier spectroscopy. The ability of the resulting polymers to molecularly recognize zinc was evaluated. Based on experimental data on static adsorption, the adsorption capacity of ZnIP and NIP was determined using an atomic emission spectrometer. It was found that ZnIP is characterized by better physical parameters and a higher ability for molecular recognition of zinc compared to NIP. ZnIP with zinc imprints were found to have better sorption capacity for zinc than their reference polymers. The sorption of zinc by molecular imprinted ZnIP is mainly due to the complex formation and pores of the initial carbon product. The synthesized ZnIP have increased porosity. The presence of pores with a diameter <50 nm in ZnIP is associated with voids formed after acid hydrolysis, which is clearly visible in images recorded by scanning electron microscopy. Thus, the possibility of using ZnIP as a selective sorbent has been established.

ТИПЫ ПОЛИМЕРОВ ДЛЯ МЕМБРАН ТОПЛИВНЫХ ЭЛЕМЕНТОВ

The work reflects a list of polymer materials used in the world to create proton-conducting mem-branes for low-temperature fuel cells. An analysis of the structure, physicochemical properties, condi-tions for the synthesis of polymers and operational characteristics of the membranes obtained on their basis was carried out

Natural and Synthetic Polymers for Biomedical and Environmental Applications.

Natural and synthetic polymers are a versatile platform for developing biomaterials in the biomedical and environmental fields. Natural polymers are organic compounds that are found in nature. The most common natural polymers include polysaccharides, such as alginate, hyaluronic acid, and starch, proteins, e.g., collagen, silk, and fibrin, and bacterial polyesters. Natural polymers have already been applied in numerous sectors, such as carriers for drug delivery, tissue engineering, stem cell morphogenesis, wound healing, regenerative medicine, food packaging, etc. Various synthetic polymers, including poly(lactic acid), poly(acrylic acid), poly(vinyl alcohol), polyethylene glycol, etc., are biocompatible and biodegradable; therefore, they are studied and applied in controlled drug release systems, nano-carriers, tissue engineering, dispersion of bacterial biofilms, gene delivery systems, bio-ink in 3D-printing, textiles in medicine, agriculture, heavy metals removal, and food packaging. In the following review, recent advancements in polymer chemistry, which enable the imparting of specific biomedical functions of polymers, will be discussed in detail, including antiviral, anticancer, and antimicrobial activities. This work contains the authors' experimental contributions to biomedical and environmental polymer applications. This review is a vast overview of natural and synthetic polymers used in biomedical and environmental fields, polymer synthesis, and isolation methods, critically assessessing their advantages, limitations, and prospects.

Synthesis and catalytic performance of One-Dimensional coordination polymers for Knoevenagel condensation under green conditions

This work presents the synthesis, characterization, and catalysis application of two one-dimensional coordination polymers. The structures were obtained through a two-step synthesis method, involving the combination of the ligands 5-sulfoisophthalic acid (ACSO3) and isonicotinylhydrazine (INH) with Zn(II), designated as 1, or Cu(II), designated as 2, resulting in a ladder-shaped topology system. Compound 1 was thoroughly characterized using single-crystal X-ray diffraction, along with complementary techniques such as FT-IR spectroscopy, elemental analysis, and thermogravimetric analysis. These analyses provided insights into its bifunctional catalytic structure. Moreover, the heterogeneous catalytic activity of compound 1 was evaluated in Knoevenagel condensation reactions using various solvents. The catalyst exhibited high conversion rates and recyclability under mild conditions, particularly noteworthy when using eco-friendly solvents, establishing it as a green catalyst. A computational simulation was conducted to explore the surface properties of 1, providing a comprehensive description of its bifunctional properties.

Development of Ring-Expansion RAFT Polymerization of tert-Butyl Acrylate with a Cyclic Trithiocarbonate Derivative toward the Facile Synthesis of Cyclic Polymers.

Polymers with cyclic topology have no terminal structure and, therefore, exhibit various unique physical and functional properties compared to those of linear analogs. In this paper, we report an innovative methodology for the synthesis of cyclic polymers via ring-expansion RAFT (RE-RAFT) polymerization of vinyl monomers using a cyclic trithiocarbonate derivative (CTTC) as a RAFT agent. RE-RAFT of tert-butyl acrylate (TBA) was performed to yield a mixture of polymers exhibiting a bimodal size exclusion chromatography (SEC) trace. Both the peak top molecular weights shifted to higher-molecular-weight regions as the monomer conversion increased. The structure of the resulting polymer mixture was examined by 1H NMR and MALDI-TOF-MS. Detailed studies indicated that the obtained polymer of higher molecular weight was one of the large-sized cyclic polymers generated by the fusion of smaller-sized cyclic polymers during the RE-RAFT polymerization process. This approach opens the door to the simple synthesis of well-controlled cyclic polymers with complex structures, such as alternating and multi-block repeat unit sequences.

Hydrothermal Synthesis of a Novel One-dimensional Cadmium-based Coordination Polymer for Effective Detection of Hazardous Chemicals

Hydrothermal Synthesis of a Novel One-dimensional Cadmium-based Coordination Polymer for Effective Detection of Hazardous Chemicals

Polystyrene containing 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate with Low Molecular Weight Used As Macroadditive Photostabilizer

Photostabilizer additives are employed to shield polymer materials from ultraviolet (UV) degradation. One category of such additives includes ultraviolet light absorbers (UVA), which absorb radiation and dissipate it within the polymer network as heat. These additives are typically incorporated into the polymer during processing, but they can pose challenges such as low miscibility and migration of the additive to the polymer's surface. A viable solution to these issues is the synthesis of polymers with additives chemically connected to the polymer chain. This work investigates the copolymerization of styrene with the additive 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate (BHEM), resulting in the formation of PS-BHEM. This copolymer was then utilized in commercial polymers (PS, HIPS, and ABS) to mitigate degradation, with a comparative analysis of its effectiveness against the commercial stabilizer Tinuvin P. The copolymerization process yields a 92 % product, and the presence of BHEM is confirmed through SEC analysis. Accelerated weather degradation tests indicate that the incorporation of PS-BHEM enhances the UV stabilization of commercial ABS without altering the mechanical properties of the polymers.

New in situ generated acylhydrazidate-coordinated complexes: Syntheses, structural characterizations and magnetic properties

The present study reports the successful synthesis of three new magnetic coordination polymers, namely [Mn(BPTH)(H2O)]n (1), [Co(BPTH)(phen)]n (2), and [Co(BPTA)(phen)(H2O)2]n (3), through a solvothermal method (H2BPTH = biphenyl-3,3′,4,4′-tetracarboxyhydrazide, H2BPTA = biphenyl-3,3′,4,4′-tetracarboxylic acid, phen = 1,10-phenanthroline). In compounds 1 and 2, the bishydrazide ligand H2BPTH is formed by in situ acylation of H2BPTA with hydrazine hydrate. All the three title compounds contain M2O2 clusters (M=Mn(1), Co(2) and Co(3)). In compound 1, the amido-oxygen atoms O1 coordinate with Mn2+ to form a Mn2O2 cluster, while the adjacent Mn2O2 cluster is interconnected by the ligand's oxygen atoms O3 and O4, resulting in an infinite expansion into a 3D network structure. Compound 2 exhibits a 1D chain structure containing Co2O2 clusters, which further extends into a 2D supramolecular layer through π···π stacking interactions. Compound 3 comprises adjacent Co2O2 clusters interconnected by oxygen atoms O1, O2, and O5 on the ligand to form a 2D layered architecture. The 2D layers are linked through intermolecular O–H···O hydrogen bonds of H2BPTA ligands to form a 3D supramolecular network. Magnetic measurements reveal weak ferromagnetic behavior for compound 1 while compounds 2 and 3 exhibit weak antiferromagnetic interactions at different temperatures. Overall, this research presents new insights into the design and synthesis of coordination polymers with diverse structures and magnetic properties.

Development of an Innovative Biosensor Based on Graphene/PEDOT/Tyrosinase for the Detection of Phenolic Compounds in River Waters.

Phenolic compounds, originating from industrial, agricultural, and urban sources, can leach into flowing waters, adversely affecting aquatic life, biodiversity, and compromising the quality of drinking water, posing potential health hazards to humans. Thus, monitoring and mitigating the presence of phenolic compounds in flowing waters are essential for preserving ecosystem integrity and safeguarding public health. This study explores the development and performance of an innovative sensor based on screen-printed electrode (SPE) modified with graphene (GPH), poly(3,4-ethylenedioxythiophene) (PEDOT), and tyrosinase (Ty), designed for water analysis, focusing on the manufacturing process and the obtained electroanalytical results. The proposed biosensor (SPE/GPH/PEDOT/Ty) was designed to achieve a high level of precision and sensitivity, as well as to allow efficient analytical recoveries. Special attention was given to the manufacturing process and optimization of the modifying elements' composition. This study highlights the potential of the biosensor as an efficient and reliable solution for water analysis. Modification with graphene, the synthesis and electropolymerization deposition of the PEDOT polymer, and tyrosinase immobilization contributed to obtaining a high-performance and robust biosensor, presenting promising perspectives in monitoring the quality of the aquatic environment. Regarding the electroanalytical experimental results, the detection limits (LODs) obtained with this biosensor are extremely low for all phenolic compounds (8.63 × 10-10 M for catechol, 7.72 × 10-10 M for 3-methoxycatechol, and 9.56 × 10-10 M for 4-methylcatechol), emphasizing its ability to accurately measure even subtle variations in the trace compound parameters. The enhanced sensitivity of the biosensor facilitates detection and quantification in river water samples. Analytical recovery is also an essential aspect, and the biosensor presents consistent and reproducible results. This feature significantly improves the reliability and usefulness of the biosensor in practical applications, making it suitable for monitoring industrial or river water.

High H-abstraction efficiency of Ni(II)-Ni(III)-Ni(II) cycle mediated oxidation of aromatic contaminants by peroxydisulfate

Peroxydisulfate (PDS) activation has attracted great attention for the treatment of aromatic contaminants in wastewater. In this study, the synthesized β-Ni(OH)2 exhibits remarkable reactivity in the catalytic oxidation of aromatic contaminants of phenol and aniline under alkaline conditions at a low molar ratio of 2:1 between the initial PDS and aromatic contaminants, indicating that the aromatic contaminants have not been completely mineralized into CO2 and H2O. By means of quenching experiments, LSV analysis and various characterizations, we rule out the primary contributions of •OH, SO4•−, O2•−, 1O2 or the non-radically activated PDS complexes to the oxidation processes. Instead, the oxidation cycle of Ni(II)-Ni(III)-Ni(II) plays the predominant role. DFT calculations further reveal the strong adsorption of phenol (-1.217 eV) and aniline (-1.166 eV) on β-NiOOH surface, which subsequently initiates H-abstraction from phenol and aniline by β-NiOOH with low interaction barriers of 0.119 eV and 0.467 eV, respectively. The produced aromatic radicals then undergo polymerization to produce phenol and aniline polymers. This work provides new insight on PDS activation and offers an effective and cost-saving approach for the removal, recycling, and synthesis of aromatic polymers.

Synthesis and Reactivity of Diazirine-Containing Polymers via Controlled Radical Polymerization

Synthesis and Reactivity of Diazirine-Containing Polymers via Controlled Radical Polymerization

Recent Advances in Polymers Bearing Activated Esters for the Synthesis of Glycopolymers by Postpolymerization Modification.

Glycopolymers are functional polymers with saccharide moieties on their side chains and are attractive candidates for biomaterials. Postpolymerization modification can be employed for the synthesis of glycopolymers. Activated esters are useful in various fields, including polymer chemistry and biochemistry, because of their high reactivity and ease of reaction. In particular, the formation of amide bonds caused by the reaction of activated esters with amino groups is of high synthetic chemical value owing to its high selectivity. It has been employed in the synthesis of various functional polymers, including glycopolymers. This paper reviews the recent advances in polymers bearing activated esters for the synthesis of glycopolymers by postpolymerization modification. The development of polymers bearing hydrophobic and hydrophilic activated esters is described. Although water-soluble activated esters are generally unstable and hydrolyzed in water, novel polymer backbones bearing water-soluble activated esters are stable and useful for postpolymerization modification for synthesizing glycopolymers in water. Dual postpolymerization modification can be employed to modify polymer side chains using two different molecules. Thiolactone and glycine propargyl esters on the polymer backbone are described as activated esters for dual postpolymerization modification.

Competition in formation of stimuli-responsive metallogel and coordination polymers from a single precursor: synthesis, characterization and catalytic application

The synthesis, structure, and catalytic properties of a new 2D crystalline coordination polymer (Zn-CP1) as well as a stable new low molecular weight metallogel (Zn-G1) are reported. Interestingly, both types of materials can be synthesized using the same amino acid based chiral ligand (PV) and Zn2+ ion. Precisely, pure organic solvent (MeOH) prompts gelation while DMF-water medium favours the formation of coordination polymer (CP). Hence, the nature of the solvents and metal counter anion used, play a crucial role in gel formation. Both the CP and gel were characterized by various spectroscopic and analytical techniques such as PXRD, FT-IR, TGA, SEM, and dynamic rheology. Structural analysis of Zn-G1 reveals an entangled spongy-like fibrous network in which spongy patches consist of micro fibres within the matrix of the supramolecular metallogel, while the structural analysis of Zn-CP1 revealed the formation of a 2D sheet-like structure. The Zn-G1 exhibits remarkable stimuli-responsive behaviour towards temperature, mechanical force, and chemicals; however, the Zn-CP1 was found to exhibit promising catalytic activity over Zn-G1 for the conversion of CO2 to cyclic carbonate from various epoxides.

The Use of an Advanced Intelligent-Responsive Polymer for the Study of Dynamic Water-Carbon Dioxide Alternating Displacement.

Addressing the issue of inadequate temperature tolerance in traditional polymers, in this study, we successfully executed a one-step synthesis of intelligent-responsive polymers which have excellent adaptability in water-gas alternating displacement scenarios. Utilizing the fatty acid method, we produced OANND from oleic acid (OA) and N,N-dimethyl-1,3-propanediamine (NND). Upon testing the average particle size in the aqueous solution both prior and subsequent to CO2 passage, it became evident that OANND assumes the form of a small-molecule particle in the aqueous phase, minimizing damage during formation. Notably, upon CO2 exposure, it promptly organizes into stable micelles with an average size of 88 nm and a relatively uniform particle distribution. This unique characteristic endows it with a rapid CO2 response mechanism and the ability to form a highly resilient gel. In the exploration of viscoelastic fluids, we observed the remarkable behavior of the AONND aqueous solution when CO2/N2 was introduced. This system displayed repeatable transitions between aqueous and gel states, with the highest viscosity peaking at approximately 3895 mPa·s, highlighting its viscosity reversibility and reusability properties. The rheological property results that we obtained indicate that an elongated micellar structure is present in the solution system, with the optimal concentration ratio for its formation determined as 0.8, which is the molar ratio of the OANND-NaOA system. In the sealing performance tests, a 1.0 wt% concentration of the gel system exhibited excellent injectability properties. At 80 °C, this gel effectively reduced the permeability of a sand-filled model to 94.5% of its initial value, effectively sealing potential leakage paths or gas fluxes. This remarkable ability to block leakage paths and reduce seepage capacity highlights the material's superior blocking effect and erosion resistance properties. Furthermore, even at a temperature of 90 °C and an injection pore volume (PV) of 3, this plugging system could reduce the permeability of a high-permeability sand-filled model to over 90% of its initial value.

Synthesis of Porous Polymer Based Solid Acid Catalyst Towards Room Temperature Thioacetal/Thioketal Formation

Synthesis of Porous Polymer Based Solid Acid Catalyst Towards Room Temperature Thioacetal/Thioketal Formation

Porous sulfur polymers for effective aqueous-phase organic contaminant removal

Sulfur polymers produced through 'inverse vulcanization' exhibit various attributes, such as photocatalytic activity and a high capacity to adsorb heavy metals. Nevertheless, there is a lack of research investigating the use of sulfur polymers as materials for the removal of organic contaminants. In this work, porous sulfur polymers (PSPs) were synthesized from elemental sulfur and 1,3-diisopropenylbenzene, with porosity introduced via salt templating. The result is a material that can strongly adsorb and chemically neutralize a model organic contaminant (caffeine). PSPs show adsorption up to 5 times higher than a leading adsorption material (activated carbon). Furthermore, either the adsorption or degradation processes can govern the removal efficiency depending on the synthesis parameters of PSPs. This is the first-ever report demonstrating sulfur polymers as effective materials for removing emerging contaminants from water. The versatile synthesis of sulfur polymers offers variation, which means that there is much more to explore in this exciting research area.

Polyurethanes by ring‐opening polymerization initiated from alcohol moiety‐tethering acylazide

AbstractAn orthogonal agent having both alcohol and acylazide groups was used to construct novel polyurethanes by a simple synthetic process. Ring‐opening polymerization (ROP) of δ‐valerolactone from the orthogonal agent afforded a crystalline polymer having acylazide initiation end, while that of δ‐decanolactone resulted in an amorphous polymer. Since acylazide groups undergo thermally induced Curtius rearrangements to yield isocyanate groups, simple heating of above polymers gave macromonomers having both an isocyanate initiation end and an alcohol termination end, which afforded corresponding polyurethane by self‐polyaddition in a bulk condition without any additives. Meanwhile, kinetic analysis of the Curtius rearrangement revealed that a quantitative conversion was reached within a short reaction time, for example at 110°C for 30 min, or at 100°C for 1 h. Moreover, obtained polyurethane species showed unique self‐immolative type thermal degradation behavior. Considering the above, this orthogonal agent turned out to be useful to construct various polyurethane structures by a facile synthetic process, which would contribute to precise polymer synthesis and sequence defined polymer synthesis.

Effect of methyl methacrylate concentrations on surface and thermal analysis of composite polymer polymethylmethacrylates with mesogen reactive RM82

ABSTRACT This research report of the synthesis of composite polymers from liquid crystal mesogen reactive (RM82) monomers with Methyl methacrylate (MMA). The purpose of this research is analysis the effect concentration of MMA on the surface and thermal of the composite polymer PMMA-RM82. The result of the morphological analysis of composite surfaces performed by polarization optical microscopy (POM) technique showed liquid crystal textures affected composition from two monomers. SEM images show that the surface of the RM82 liquid crystal has a shape resembling fibrous and blade-like crystals with a length of up to 10 μm (micrometers). Analysis thermal showed the heat released by the PMMA-RM82 increased with the increase in MMA weight percent. This affects the rapid crystallization process of PMMA-RM82 which of concentration MMA 30%-RM82 the heat released is almost twice as much as the heat released by MMA 5%-RM82. The absence of PMMA and RM82 peaks both endothermic and exothermic in PMMA-RM82 samples indicates that polymerization has occurred and a new product has formed. Analysis structure molecule by FTIR found that the IR spectral form of each variation in the weight percent of MMA was almost the same, but there was a spectral shift that showed that polymerization had occurred in PMMA-RM82 which was characterized by a reaction to the free radical C=C bond released by the photoinitiator. XRD pattern of composite PMMA-RM82 showed the peaks formed are located at scattering angles similar to RM82 but there is a decrease in intensity as the percent weight of MMA increases.