Copolymer Composition Research Articles

Enhanced antifouling PSE hollow fiber membrane via zwitterionic copolymer segregation

Blending hydrophilic additives is an effective method to improve the surface hydrophilcility and antifouling property of ultrafiltration membranes. In this study, we prepared a series of polysulfate (PSE) hollow fiber membranes (HFMs) containing a zwitterion-based copolymer, poly(4-vinylpyridine-co-methylacryloxyethyl phosphocholine), with varying monomer ratios and blending quantities. The relationship between cast solution properties and phase separation behavior was investigated, as well as the impacts of copolymer composition and amount on the separation performances and antifouling abilities of the membranes. A higher hydrophilic monomer ratio and more copolymer addition of zwitterionic copolymer would facilitate surface segregation, increasing the hydrophilicity of membrane surface and generating a dense hydration layer. This layer can resist macromolecule contaminants and promote water molecular transport. Furthermore, a more compacted skin layer improves separation ability. The optimized PSE HFMs had water fluxes around 140 L m−2 h−1, BSA rejections over 97 %, and flux recovery rates over 92 % during operation. Moreover, the membrane demonstrated ultra-low flux-sacrifice when applied to protein solutions while maintaining a high rejection rate, which indicates the distinctive and strong competitiveness of PSE/P(4VP-co-MPC) HFMs.

Modeling of Chain Sequence Length and Distribution in Random Copolyesters.

The performances and properties of random copolyesters, including biodegradability, mechanical and thermal properties, transparency, etc., are highly influenced by their chain structures. However, obtaining detailed chain sequence information remains a significant challenge. This study introduces a mathematical model based on a probabilistic approach to determine the sequence length and distribution in random copolyesters. Two types of copolyesters, A1A1BB-A2A2BB, representing poly(butylene adipate-co-terephthalate) (PBAT), and A1A1B1B1-A2B2, using poly(butylene succinate-co-glycolic acid) (PBT-PGA) as an example, are the focus. The predicted sequence lengths of various copolyesters derived from the model are in good agreement with the values reported in the literature. The chain sequence distribution obtained from the model provides better insights into the unique properties of the copolyesters. It is observed that the incorporation of hydroxyl acid units into copolyester chains effectively reduces the sequence length without altering the copolymer composition, offering a strategic approach for enhancing degradation performance while maintaining mechanical properties of random copolyesters. The influence of the number-average sequence length becomes particularly significant when the copolymer composition ranges between 0.7 and 0.9, with a higher copolymer composition required for copolyesters containing hydroxyl acid monomer units. This model represents a powerful tool for researchers, enabling a deeper understanding of the relationship between copolymer composition and its structural characteristics in random copolyesters and facilitating the development of high-performance random copolyesters.

Hydrogel granular systems for controlled release based on (co)polymers of 2-hydroxyethyl methacrylate with polyvinylpyrrolidone (a review)

The development of polymer carriers for systems of prolonged and controlled release of substances, particularly drugs, into the action environment is a relevant task in polymer chemistry and technology. This aims to solve the problem of reducing the effective dose of a medical drug administered into the body of a person or animal. The latest achievements in the field of creating such carriers in the form of spherical particles based on 2-hydroxyethyl methacrylate and polyvinylpyrrolidone (co)polymers are analyzed and summarized. The working principles and advantages of such systems are described. The research of the synthesis regularities, structure, properties and perspectives of application of granular hydrogels based on 2-hydroxyethyl methacrylate and its copolymers with polyvinylpyrrolidone was analyzed. The mixture of decanol and cyclohexanol as a solvent for the monomer phase is substantiated. Based on the analysis of kinetic studies, the optimal technological parameters for the suspension polymerization of 2-hydroxyethyl methacrylate with polyvinylpyrrolidone were selected, and the possibility of regulating the dispersion characteristics of copolymers via changes in the technological synthesis modes was confirmed. The results of studies on the sorption-desorption properties of copolymers concerning model substances and drugs are described. The possibility of directed regulation of sorption capacity and drug release rate through changes in copolymer composition was confirmed. Methods for increasing the sorption capacity of hydrogels for drugs are proposed.

Formation of Superhydrophobic Coatings Based on Dispersion Compositions of Hexyl Methacrylate Copolymers with Glycidyl Methacrylate and Silica Nanoparticles.

In the last decade, the task of developing environmentally friendly and cost-effective methods for obtaining stable superhydrophobic coatings has become topical. In this study, we examined the effect of the concentrations of filler and polymer binder on the hydrophobic properties and surface roughness of composite coatings made from organic-aqueous compositions based on hexyl methacrylate (HMA) and glycidyl methacrylate (GMA) copolymers. Silicon dioxide nanoparticles were used as a filler. A single-stage "all-in-one" aerosol application method was used to form the coatings without additional intermediate steps for attaching the adhesive layer or texturing the substrate surface, as well as pre-modification of the surface of filler nanoparticles. As the ratio of the mass fraction of polymer binder (Wn) to filler (Wp) increases, the coatings show the lowest roll-off angles among the whole range of samples studied. Coatings with an optimal mass fraction ratio (Wn/Wp = 1.2 ÷ 1.6) of the filler to polymer binder maintained superhydrophobic properties for 24 h in contact with a drop of water in a chamber saturated with water vapor and exhibited roll-off angles of 6.1° ± 1°.

DEVELOPMENT OF A DEPRESSOR ADDITIVE BASED ON BIODEGRADABLE CHITOSAN FOR DIESEL FUEL

For the first time in scientific research, effective compositions of copolymers based on environmentally friendly aminopolysaccharide chitosan and acrylic acid and styrene were developed and scientifically based. The scientific significance of the research results was explained by the fact that a copolymer was obtained from acrylic and styrene.

Free radical copolymerization kinetics of bio-based dibutyl itaconate and n-butyl acrylate

The free radical copolymerization of dibutyl itaconate (DBI), a monomer derived from renewable resources, and n-butyl acrylate (BA) is investigated to explore the potential of incorporating itaconate monomers into commercial acrylic resins to enhance the sustainability of coating materials. Batch experiments were conducted at 50 °C and 80 °C, varying initial monomer and initiator concentrations as well as monomer compositions, with proton NMR and size exclusion chromatography used to analyze monomer conversion profiles and polymer molar mass distributions (MMDs). The data were analyzed using a kinetic model developed to guide the experimental studies and estimate key kinetic parameters controlling copolymer composition, polymerization rate and polymer MMDs. The use of the more reactive BA as comonomer significantly increases the conversion and molar mass of the resulting copolymer. Furthermore, semi-batch operating conditions similar to current industrial practice can incorporate a substantial fraction of DBI into acrylic copolymer resins, thus enhancing their sustainability profile.

Nonmonotonic Impact of Statistical Copolymer Composition on the Kinetics of Capillary Rise Infiltration

Nonmonotonic Impact of Statistical Copolymer Composition on the Kinetics of Capillary Rise Infiltration

Complexes of polymeric acids and short polyamines as binary stimulus-sensitive systems

Stimulus-sensitive polymers are of great interest due to their unusual properties in solution and diverse applications. Copolymers with different groups (hydrophilic, hydrophobic and ionizable) are typical stimulus-sensitive polymers, and varying the copolymer composition allows the pH and thermal sensitivity to be adjusted for a particular application. We found that complexes of polymeric acids with short methylated polyamines having trimethylene insertions between amine groups exhibit stimulus-sensitive properties in aqueous media at moderate pH and temperature. The position of the lower critical temperature of the solution depends on the ratio of polyacid to polyamine and on the pH. The complex of poly(acrylic acid) and pentaamine was found to be electrosensitive: exposure to an electric field with reversible polarity (8 Hz) led to precipitation of the polymer. These binary stimulus-sensitive compositions consist of two simple substances and are a promising alternative to copolymer-based systems, since the adjustment of properties does not require the synthesis of new substances and expensive toxicological studies in the case of biomedical applications.

Multicomponent Self-Assembly and Self-Sorting of Polymer Micelles in Water: Selective and Switchable Association by Kinetic or Thermodynamic Control.

Herein, we report multicomponent self-assembly and self-sorting of polymer micelles in water using mixtures of an anionic random copolymer bearing sodium sulfonate and dodecyl groups and random copolymers carrying poly(ethylene glycol) (PEG) and alkyl groups. In pure water, the anionic copolymer is co-self-assembled with the PEG copolymers to form anion/PEG-fused micelles with a controlled aggregation number. By designing the composition or alkyl groups of PEG copolymers, the fused micelle is reversibly self-sorted into discrete anion or PEG micelles in the presence of NaCl. Co-self-assembly of the anionic copolymer and PEG copolymers is kinetically or thermodynamically controlled, depending on the dynamic properties of the PEG copolymer micelles. Thus, the selective self-assembly of ternary copolymers is also controllable and switchable by temperature: A kinetically favored anion/PEG-fused micelle is predominantly formed in the presence of a kinetically frozen PEG micelle at low temperature, whereas the fused micelle is transformed via polymer chain exchange upon heating into a thermodynamically more stable anion/PEG-fused micelle.

In Situ Formation of Acidic Comonomer during Thermal Treatment of Copolymers of Acrylonitrile and Its Influence on the Cyclization Reaction.

Binary and ternary copolymers of acrylonitrile (AN), tert-butyl acrylate (TBA), and n-butyl acrylate (BA) are synthesized through conventional radical polymerization in DMSO in the presence of 2-mercaptoethanol. The thermal behavior of binary and ternary copolymers is studied under argon atmosphere and in air. It is demonstrated that the copolymers of AN contain 1-10 mol.% of TBA split isobutylene upon heating above 160 °C, resulting in the formation of the units of acrylic acid in the chain. The carboxylic groups formed in situ are responsible for the ionic mechanism of cyclization, which starts at lower temperatures compared with pure polyacrylonitrile (PAN) or AN copolymer with BA. The activation energy of cyclization through ionic and radical mechanisms depends on copolymer composition. For the ionic mechanism, the activation energy lies in the range ca. 100-130 kJ/mole, while for the radical mechanism, it lies in the range ca. 150-190 kJ/mole. The increase in the TBA molar part in the copolymer is followed by faster consumption of nitrile groups and the evolution of a ladder structure in both binary and ternary copolymers. Thus, the incorporation of a certain amount of TBA in PAN or its copolymer with BA allows tuning the temperature range of cyclization. This feature seems attractive for applications in the production of melt-spun PAN by choosing the appropriate copolymer composition and heating mode.

Characterization of Mechanical Properties and Surface Wettability of Epoxy Resin/Benzoxazine Composites in a Simulated Acid Rain Environment

Despite the robustness of thermosetting coatings in various applications, prolonged exposure to acidic environments can cause gradual deterioration, leading to structural or functional damage. This study investigates composite materials comprised of cycloaliphatic epoxy resin (CER) and benzoxazine (BZ) at three different weight ratios: 50:50, 25:75, and 0:100. These composites were exposed to nitric acid, simulating acid rain, for durations ranging from 1 to 5 h. The specimens were characterized for weight change, mechanical properties (flexural strength and short beam strength), and surface properties (contact angle and contact angle hysteresis). Although minimal changes in the physical and mechanical properties of both homopolymer and copolymer composites were detected after short acid exposure (up to 5 h), surface wettability analysis via static contact angle and contact angle hysteresis revealed more pronounced deterioration. The static contact angle decreased by 24.96% and 28.32% for homopolymer BZ and copolymer BZ-CER composites, respectively. Contact angle hysteresis increased by 19.39% and 27.80% for 5 h acid-exposed homopolymer BZ and copolymer CER, respectively. This study underscores the utility of surface wettability analysis as a valuable tool for monitoring deterioration from acidic aging in polymers, particularly in BZ-CER systems used in structural and high-performance applications.

Thermally-responsive dismantlable adhesion system for steel plates using methacrylate copolymers containing a tert-butoxycarbonyl group

A drastic change in the bulk properties of adhesive materials as well as a reduction of interfacial interaction is an important key for the development of dismantlable adhesion systems, i.e., reliable bonding systems with a function of on-demand debonding. The deprotection of tert-butoxycarbonyloxy (BOC) groups included in adhesive polymers can be applied to the construction of a dismantlable adhesion system for steel plates combined with acrylic and epoxy adhesives. In this study, we evaluated the adhesive properties of the copolymers of 2-(tert-butoxycarbonyloxy)ethyl methacrylate (BHEMA), glycidyl methacrylate (GMA), and 3-trimethoxysilylpropyl methacrylate (SMA) for the dismantlable bonding of steel plate cold commercial (SPCC). Spontaneous dismantling of the SPCC adhesive structures was achieved after heat treatment under the conditions at 210 °C for 15 min when the BHEMA/GMA/SMA copolymers with an appropriate copolymer composition were used as the acrylic adhesives or the primers for epoxy adhesion. We discuss the interfacial interactions between the adherend and the adhesives for reliable adhesion and the effects of the deprotection of the BOC groups for dismantling to exhibit both an adhesion strength required for metal bonding and a rapid decrease in the strength by thermal stimulus.

Synthesis and Investigation of Polymers Containing Different Ratio of Quinonediiminic and Benzenoid Units in PANi‐Like Structure

AbstractThis study presents, for the first time, a new method for the synthesis of polymers containing different ratios of oxidized quinoid and reduced benzenoid units in polyaniline (PANi)‐like structure. Copolymers were synthesized by an oxidative copolymerization method of p‐phenylene diamine (p‐PDA) and o‐anisidine (o‐An) in an organic medium using different initial compositions of monomers. The compositions of the copolymer were determined based on 1H NMR spectral data. The thermal stability, electrical conductivity, morphology, and solubility were studied and a comparative analysis with polyaniline and corresponding homopolymers was been carried out. The thermal behavior of copolymers was studied using thermogravimetric analysis and differential scanning calorimetry. It was found that during heating one endothermic process of water evaporation and two exothermic processes occur, which depend on copolymer composition, and only 30% weight loss occurs up to 600 °C. It is shown that room‐temperature conductivity of copolymers doped with hydrochloric and sulfuric acids ranges from 10−5 to 10−3 S cm−1 and increases with increasing concentration of o‐anisidine structural units. The conductivity of iodine‐doped copolymers is of the same order as the conductivity of iodine‐doped PANi in emeraldine and leucoemeraldine forms. The morphology of doped copolymers depends on the co‐monomer ratio and the type of dopants.

Alkaline-Responsive, Self-Healable, and Conductive Copolymer Composites with Enhanced Mechanical Properties Tailored for Wearable Tech.

Despite significant advancements, current self-healing materials often suffer from a compromise between mechanical robustness and functional performance, particularly in terms of conductivity and responsiveness to environmental stimuli. Addressing this issue, the research introduces a self-healable and conductive copolymer, poly(ionic liquid-co-acrylic acid) (PIL-co-PAA), synthesized through free radical polymerization, and further optimized by incorporating thermoplastic polyurethane (TPU). This combination leverages the unique properties of each component, especially ion-dipole interactions and hydrogen bonds, resulting in a material that exhibits exceptional self-healing abilities and demonstrates enhanced mechanical properties and electrical conductivity. Moreover, the PIL-co-PAA/TPU films showcase alkaline-responsive behavior, a feature that broadens their applicability in dynamic environments. Through systematic characterization, including thermogravimetric analysis, tensile testing, and electrical properties measurements, the mechanisms behind the improved performance and functionality of these films are elucidated. The conductivities and ultimate tensile strength (σuts) of the PIL-co-PAA/TPU films regain 80% under 8h healing process. To extend the applications for wearable devices, the self-healing properties of commercial cotton fabrics coated with the self-healable PIL-co-PAA are also investigated, demonstrating both self-healing and electrical properties. This study advances the understanding of self-healable conductive polymers and opens new avenues for their application in wearable technology.

The flame retardant cyclic olefin copolymer composites with boric acid modified ZSM-5 synergists

The flame retardant cyclic olefin copolymer composites with boric acid modified ZSM-5 synergists

Amphiphilic diblock copolymers of polyisobutylene-b-poly(2-ethyl-2-oxazoline) via cationic polymerization

A series of amphiphilic polyisobutylene-b-poly (2-ethyl-2-oxazoline) (PIB-b-PEOX) diblock copolymer/Ag nanoparticle composites were successfully in-situ synthesized via cationic ring-opening polymerization of 2-ethyl-2-oxazoline (EOX) with high initiation efficiency by using allyl bromide end functionalized polyisobutylene (PIB-allylBr) as a macroinitiator and AgClO4 as a coinitiator. The microphase separation formed in the resulting PIB-b-PEOX diblock copolymers due to the thermodynamic imcompability of hydrophilic PEOX segments and hydrophobic PIB segments. The micromorphology of phase separation is dependent on the copolymer composition, in which sea-island micromorphology formed for PIB118-b-PEOX80 and bicontinuous phase micromorphology formed for PIB118-b-PEOX97. The micelles with nano-scale size in the range of 15–80 nm and having high drug loading rate of ca. 48.9 % can be formed by self-assembly of the amphiphilic diblock copolymers in n-hexane. The drug cumulative release rate can be increased with an increase in the proportion of PEOX segments, due to the strong interaction between ibuprofen and the PEOX segments. The hydrophilicity of the PIB-b-PEOX diblock copolymer surfaces can be improved after ethanol vapor induction. The PIB-b-PEOX diblock copolymers behave biocompatibility and good anti-protein adsorption property. The amphiphilic PIB-b-PEOX diblock copolymer/Ag nanoparticle composites exhibit high antibacterial efficiency for Gram-negative bacterium (E. coli) and Gram-positive bacterium (S. aureus). To the best of our knowledge, this is the first example of PIB-b-PEOX diblock copolymer/Ag nanoparticle (6.4 ± 2.6 nm) composites synthesized in-situ with good biocompatibility, anti-protein adsorption, and antibacterial properties, which would have potential applications for drug delivery and anti-protein coating in biomedical areas.

Partially Bio-Based and Biodegradable Poly(Propylene Terephthalate-Co-Adipate) Copolymers: Synthesis, Thermal Properties, and Enzymatic Degradation Behavior.

A series of partially bio-based and biodegradable poly(propylene terephthalate-co-adipate) (PPTA) random copolymers with different components were prepared by the melt polycondensation of petro-based adipic acid and terephthalic acid with bio-based 1,3-propanediol. The microstructure, crystallization behavior, thermal properties, and enzymatic degradation properties were further investigated. The thermal decomposition kinetics was deeply analyzed using Friedman's method, with the thermal degradation activation energy ranging from 297.8 to 302.1 kJ/mol. The crystallinity and wettability of the copolymers decreased with the increase in the content of the third unit, but they were lower than those of the homopolymer. The thermal degradation activation energy E, carbon residue, and reaction level n all showed a decreasing trend. Meanwhile, the initial thermal decomposition temperature (Td) was higher than 350 °C, which can meet the requirements for processing and use. The PPTA copolymer material still showed excellent thermal stability. Adding PA units could regulate the crystallinity, wettability, and degradation rate of PPTA copolymers. The composition of PPTA copolymers in different degradation cycles was characterized by 1H NMR analysis. Further, the copolymers' surface morphology during the process of enzymatic degradation also was observed by scanning electron microscopy (SEM). The copolymers' enzymatic degradation accorded with the surface degradation mechanism. The copolymers showed significant degradation behavior within 30 days, and the rate increased with increasing PA content when the PA content exceeded 45.36%.

Surface‐Reengineering of BNNs@Hydrocarbon Polymer Composites for Ultra‐Low Dielectric Constant for High‐Frequency Applications

AbstractThis research investigates the synthesis and evaluation of cyclic olefin copolymer (COC) composites with surface‐engineered boron nitride nanosheets (BNNs) at various concentrations. The study focuses on the impact of Cetyltrimethylammonium bromide (CTAB) on BNNs′ surface functionalization to improve their dispersion within the COC matrix, including its dielectric behavior, dielectric breakdown strength, thermal management capabilities, hygroscopic properties, and mechanical robustness. The methodological approach adopted for the fabrication of COC/BNNs hybrid composites commenced with the synthesis of BNNs, surface functionalization of BNNs, in‐situ mixing and hot‐press. This step aimed to enhance compatibility and adhesion between BNNs and the COC matrix, facilitating more homogeneous nanofiller dispersion. The investigative scope of this study encompassed a rigorous evaluation of the resultant composites, with a particular emphasis on their dielectric properties. The dielectric constant (ϵ′) and loss tangent (δ) were measured at a frequency of 10 GHz, revealing an ultra‐low dielectric constant of 1.28, an exceptionally minimal loss tangent of 0.000146, a remarkable 327% (In‐plane) & 129% (axial) increase of thermal conductivity, significant improvement of dielectric breakdown strength up to 88.4 mV/mm, and low water absorptions observed. These results indicate the potential of COC/BNNs composites for high‐frequency electronic packaging applications requiring low dielectric constants.

Determination of Reactivity Ratios of N-butyl Acrylate/methyl Methacrylate Copolymerization by NMR Spectroscopy

In this study, the reactivity ratios of n-butyl acrylate (BA) and methyl methacrylate (MMA) were investigated. The copolymerization reactions were performed in toluene at 70 oC, using azobisisobutyronitrile as the initiator. The composition of the initial monomer mixture and copolymers was easily determined with the help of proton nuclear magnetic resonance (1H-NMR) spectroscopy. The molar fractions of BA and MMA in the feed were varied to apply the linear methods of Fineman–Ross and Kelen - Tudos. The calculation gave the reactivity ratios and . The computed copolymer composition was relatively close to the real copolymers obtained, with a 5% deviation.

Evaluating the operational properties of concrete admixtures containing molecularly modified polycarboxylate superplasticizers

The objective of this study focused on the design and preparation of a molecularly modified polycarboxylate superplasticizer to develop concretes with enhanced engineering features. For this purpose, polyethylene glycol was chemically modified with maleic anhydride to give the mono polyethylene glycol maleate (MPEGM). Then, polycarboxylate superplasticizer comprising of isoprenyl oxy polyethylene glycol (TPEG) and acrylic acid (AA, PCE-1), and the synthesized MPEGM with TPEG and AA (PCE-2) were prepared through solution radical polymerization. Subsequently, concrete mixtures with different dosages (0, 0.1, 0.15, 0.2, 0.25, 0.3 wt%) of PCE-1 and PCE-2 were prepared. Chemical structure of the synthesized MPEGM and superplasticizers together with their copolymer composition were identified by FTIR and 1HNMR analyses. The molecular weights (Mw) and molecular weight distributions (PDI) of PCE-1 (8.74 × 104, 1.36) and PCE-2 (8.74 × 104, 2.19) were studied by GPC analysis, respectively. The zeta potential of cement particles (2.8 mV) becomes negative in the presence of 0.6 g/L of PCE-1 (− 7.8) and PCE-2 (− 9.5). This implies that electrostatic and steric hindrance forces of adsorbed superplasticizers synergistically provide a situation for appropriate dispersion of cement particles. The results of water-reducing percentage, fluidity, air content, bleeding water rate, initial and final setting times, wet density, flexural and compressive properties, and ultrasonic pulse velocity analyses exhibit significant enhancement on the features of concrete mixtures made of polycarboxylate superplasticizer. The superiority of PCE-2 to PCE-1 was connected to its adsorption-dispersibility potent induced by stronger electrostatic and steric repulsion forces, which result in quality and continuity enhancement in concretes.