Terpolymer Composition Research Articles

Development of functional materials based on new high content electron withdrawing groups terpolymer composites for potential applications

Development of functional materials based on new high content electron withdrawing groups terpolymer composites for potential applications

Green crosslinking strategy for ethylene-vinyl acetate rubber composites with NH2-POSS as a crosslinking agent and reinforcing nanofiller

Ethylene-vinyl acetate rubber is extensively utilized in various fields including electrical wires and cables, automotive, and electronic components. Traditional peroxide vulcanization methods, however, release volatile organic compounds, posing environmental pollution concerns. To address this, 3-amino-polyhedral oligomeric silsesquioxane (NH2-POSS) was synthesized through hydrolytic condensation and used both as a crosslinking agent and a filler in the preparation of ethylene-vinyl acetate-glycidyl methacrylate terpolymer (EVM-GMA) composites. Notably, NH2-POSS not only effectively crosslinks EVM-GMA, but also thus promotes the dispersion of the silica in the composites. EVM-GMA/silica composites crosslinked by NH2-POSS display superior mechanical properties and thermal stability compared to EVM-GMA/silica composites crosslinked by organic peroxide. EVM-GMA composite with 4.5 phr NH2-POSS and 30 phr SiO2 has a tensile strength of 10.7 MPa and an elongation at the break of 240 %. This study introduces a novel and environmentally friendly crosslinking strategy for producing high-performance EVM-GMA composites without additional additives.

Bulk Free Radical Terpolymerization of Butyl Acrylate, 2-Methylene-1,3-Dioxepane and Vinyl Acetate: Terpolymer Reactivity Ratio Estimation.

This investigation introduces the first estimation of ternary reactivity ratios for a butyl acrylate (BA), 2-methylene-1,3-dioxepane (MDO), and vinyl acetate (VAc) system at 50 °C, with an aim to develop biodegradable pressure-sensitive adhesives (PSAs). In this study, we applied the error-in-variables model (EVM) to estimate reactivity ratios. The ternary reactivity ratios were found to be r12 = 0.417, r21 = 0.071, r13 = 4.459, r31 = 0.198, r23 = 0.260, and r32 = 55.339 (BA/MDO/VAc 1/2/3), contrasting with their binary counterparts, which are significantly different, indicating the critical need for ternary system analysis to accurately model multicomponent polymerization systems. Through the application of a recast Alfrey-Goldfinger model, this investigation predicts the terpolymer's instantaneous and cumulative compositions at various conversion levels, based on the ternary reactivity ratios. These predictions not only provide crucial insights into the incorporation of MDO across different initial feed compositions but also offer estimates of the final terpolymer compositions and distributions, underscoring their potential in designing compostable or degradable polymers.

1,3-Pentadiene-Assistant Living Anionic Terpolymerization: Composition Impact on Kinetics and Microstructure Sequence Primary Analysis.

The combination of a living anionic technology and a unique alternating strategy provided an exciting opportunity to prepare novel and well-defined poly(1,3-pentadiene-co-syrene-co-1,1-diphenylethylene) resins consisting of three alternating sequences of modules (A/B/C zwitterions). "A" being Styrene (St)/1,3-pentadiene (PD), "B" being diphenylethylene (DPE)/PD, "A" being DPE/St, respectively, A wide composition range of new polyolefin resins, i.e., poly (A-co-B), poly (A-co-C), and poly (B-co-C), with controlled molecular weight and very narrow molecular weight and composition distributions have been prepared by a one-pot living characteristic method. In the section of kinetic analysis, the terpolymer yields and kinetic parameters were strongly dependent on the feed/comonomer ratio as well as the content of the alternating structure. The competition copolymerization behaviors of A/B, B/C, and A/C were studied in detail in this work. By contrast, the microstructure and the thermal property of the resulting terpolymer were investigated via Nuclear magnetic resonance (NMR) and Differential scanning calorimetry (DSC) analysis. The results of 1H NMR tracking the change of [Aromatic ring]/[C=C] value indicated the distinctive copolymer-ization behavior of the selective "alternating-modules". The glass transition temperature (Tg) was very sensitive to the terpolymer composition. By contrast to poly(A-ran-B) with only one obvious Tg, there were two Tgs in the A/C and B/C copolymerization cases. Moreover, the desirable high Tg ~ 140 °C resin was limited to the terpolymers with up to 50 mol % DPE. Finally, the "ABC-X" mechanism was proposed to interpret the unique terpolymerization behavior, which belongs to the classical "bond-forming initiation" theory.

Sustainable Synthesis of CO2-Derived Polycarbonates from the Natural Product, Eugenol: Terpolymerization with Propylene Oxide

Recent years have witnessed tremendous efforts by chemists around the globe for synthesizing sustainable polymers from natural product-based building blocks (monomers). This transition is strongly motivated by the continuous accumulation of non-biodegradable oil-based polymers in the ecosystem, along with long-term goals such as economic and exhaustion of these non-renewable feedstocks. Herein, we report the synthesis of novel terpolymers obtained from the catalytic coupling of renewable eugenol epoxide (EuO), propylene oxide (PO), and CO2 using the well-defined binary (salen)CoTFA/PPNTFA (1) catalyst system. The composition of these polycarbonate terpolymers depends on the relative ratios of EuO and PO employed. To understand the mechanistic details during these terpolymerization reactions, Fineman-Ross analysis of these polymerization reactions were performed. This analysis revealed the reactivity ratios for eugenol epoxide (EuO)/PO to be rEuO = 1.95 and rPO = 0.28, respectively, which in turn reflect both the binding constants of the epoxides to the cobalt center as well as the rate constants for the ring-opening process. Further, the effect of CO2 pressure on the terpolymerization reactions was carried out which confirmed that at ambient pressure (0.1 MPa), only cyclic carbonates were obtained. The thermal analysis of these terpolymers reveals a gradual increase in the Tg values with increase in the eugenol epoxide proportion in the terpolymer. We have also employed a one pot, two step protocol for making EuO/PO based block copolymers.

Изучение влияния температуры и продолжительности гидротермального воздействия на устойчивость акрилатных терполимеров

Dynamic light scattering, capillary viscometry, and IR-Fourier spectroscopy have been used to study the effect of temperature and duration of hydrothermal exposure on the chemical composition and structure of acrylate ionic terpolymers of acrylamide (AA), acrylonitrile (AN), and sodium salt 2- acrylamide-2-methylpropanesulfonic acid (AMPSNa) AA-AN- AMPSNa. It has been established that an increase in the duration and temperature of exposure increases the effect of thermo- hydrolysis on the colloidal characteristics of the terpolymer, namely, the average hydrodynamic size of the solvated macromo- lecular polymer coils decreases. A relationship has been established between the chemical composition and structure of the initial terpolymer and the chemical composition and structure of polymer fragments formed after hydrothermal exposure. It has been determined that the increase in stability during thermohydrolysis is associated with the presence of nitrile and sulfo- nate substituents in the side groups of the polymer chain. It has been shown that the AA and AN units of the acrylate terpoly- mer are primarily subjected to thermal treatment. A noticeable change in the composition of the terpolymer after thermohy- drolysis is observed for 5 hours at an exposure temperature of 180 °C, and for 3 hours at 200 °C.

Terpolymer-Based Anion Exchange Membranes: Effect of Pendent Hexyl Groups on Membranes Properties

Abstract In the pursuit of better functioning anion exchange membranes, pendent hexyl side chains were introduced onto terpolymers composed of perfluorohexylene (PHB), hexafluoroisopylidene (BAF), and quaternized fluorene groups. The resulting QBPHBA membranes exhibited similar water absorbability and gas (hydrogen and oxygen) permeability to those of the previous terpolymer-based AEMs without aliphatic side chains. In contrast, hexyl groups contributed to improving the OH− conductivity. The highest OH− conductivity (163 mS cm−1 at 80 °C) was achieved with the QBPHBA membrane with 2.49 meq. g−1 of ion exchange capacity (IEC). Furthermore, mechanical properties were also improved; the strain at break increased from 12% (BAF-containing copolymer membrane) to 284%. The terpolymer composition for the best-balanced properties turned out to be 17 mol% of the side-chain substituted PHB groups, in particular, with high IEC (2.49 meq. g−1).

Composition-Tolerant Terpolymers for Efficient, Nonhalogenated Solvent-Processed Polymer Solar Cells

The design of terpolymers is a compelling strategy to improve the polymer solar cell (PSC) performance. However, the terpolymer composition at which the power conversion efficiency (PCE) of associated PSCs is typically optimized generally falls within a very narrow range, complicating the reproducible fabrication of optimal PSCs. In this study, a series of D–A1–D–A2 type random terpolymers (DTTz-X, where X = 10–60) is designed with structurally similar A1 and A2 accepting units. The sulfur atom of the benzothiadiazole subunit in the A1 (DTBT) unit is replaced by a nitrogen atom in the A2 (DTTz) unit, enabling the introduction of an alkyl solubilizing group while maintaining the overall structural properties of the terpolymer system. Consequently, the DTTz-X PDs maintain good optoelectronic properties at various A1/A2 ratios, while their processability in nonhalogenated solvents is significantly enhanced. Accordingly, the PSC performance of the terpolymer system shows good composition tolerance; i.e., the terpolymer system affords PSCs with PCEs exceeding 15% (up to 16.4%) over a broad range of DTTz compositions (10–40 mol %). This study establishes a useful design strategy for the development of efficient terpolymer donors for reproducible and eco-friendly fabrication of high-performance PSCs.

Development of polymeric electrolytes for fuel cells: Synthesis and characterization of new sulfonated polystyrene-co-acrylonitrile-co-butyl acrylate terpolymers

To improve the physical and chemical properties of styrene-derived polymers, new polystyrene-co-acrylonitrile-co-butyl acrylate terpolymers were synthesized and subsequently sulfonated. Six terpolymer compositions were prepared under mass radical polymerization conditions and further sulfonated to promote proton conductivity. The terpolymers were characterized by Fourier Transformed Infrared Spectroscopy (FTIR), proton and carbon nuclear magnetic resonance spectroscopy (1H NMR and 13C NMR), Gel Permeation Chromatography (GPC), Thermomechanical Analysis (TMA), Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC) and Electrochemical Impedance Spectroscopy (EIS). All synthesized terpolymers have molecular weights over 160,000 g/mol and solubility on several organic solvents. Terpolymers also showed high thermal stability by TGA and comonomers reduced Tg transitions and complex moduli along BuA content; the complex moduli clearly increased with ACN content. Intermediate aliquots taken during the sulfonation reaction were characterized indicate that incorporation of the sulfonic group decreases the thermal stability from over 350 °C in terpolymers down to 150 °C after sulfonation. The degree of sulfonation analyzed by TGA ranged between 11.2 and 15.9% leading to a proton conductivity interval from 2.9 to 4.0 mS/cm. The results suggest a lateral crosslinking reaction through sulfone groups. The proton ion conductivity values obtained are similar to those of commercially available membranes described in the literature.

Direct measurement of electrocaloric effect in P(VDF-TrFE-CFE) film using infrared imaging

Poly (vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) P(VDF-TrFE-CFE) is a relaxor ferroelectric polymer, which exhibits a temperature-independent electrocaloric effect at room temperature. In this work, the electrocaloric effect in P(VDF-TrFE-CFE) film was directly analysed using infrared imaging. P(VDF-TrFE-CFE) 64.8%/27.4%/7.8% (in mole) film of (15 ± 1) μm thickness was deposited on polyethylene naphthalate substrate. Direct ECE of P(VDF-TrFE-CFE) film was measured from 15 to 35 °C at different electric fields. A maximum adiabatic temperature change (ΔTad) of 3.58 K was measured during the cooling cycle at a field of 100 V/μm at 30 °C. Finite element analysis of temperature dissipation through the sample estimated that the actual temperature change within P(VDF-TrFE-CFE) film was 4.3 K. Despite the thermal mass of the substrate, a substantial ECE was observed in P(VDF-TrFE-CFE) films. This electrocaloric terpolymer composition could be of interest for electrocaloric cooling applications.

Infl uence of the nature of the fl uorinated monomer in the composition of organic-inorganic terpolymers containing nanostructured poly(titanium oxide) on the properties of their surface

To increase the surface hydrophobicity of organic-inorganic copolymers containing nanostructured polytanoxide, they were modifified with flfluorine-containing monomers which were introduced into the composition of the monomer mixture, followed by polymerization-polycondensation. The flfluorinated monomers used were 2,2,3,3,4,4,5,5-octaflfluoropentylacrylate, 1,1,1,3,3,3-hex aflfluoroisopropylacrylate, 2,2,3,3-tetraflfluoropropylmethacrylate. The surfaces of the synthesized terpolymers were examined by X-ray flfluorescence analysis and atomic force microscopy. The inflfluence of the nature of the third monomer on the content of titanium and flfluorine atoms in the surface layer and in the chips of the samples as well as on the topography of their surface was determined. The difference in the elemental composition affects the initial hydrophobicity of the samples surface and their ability to hydrophilize the surface under UV exposure. Terpolymers with 1,1,1,3,3,3-hexaflfluoroisopropylacrylate links exhibit the highest wetting angle - 102° - in the absence of UV exposure. However, the "hydrophobicity-hydrophilicity" switching mode is most clearly seen in the terpolymers with 2,2,3,3,4,4,5,5-octaflfluoropentylacrylate links when the wetting angle can be reversibly changed from 86° to 10°.

Effects of plastic deformation and failure on the folding behavior of non‐crosslinked ethylene propylene diene terpolymer composites

Effects of plastic deformation and failure on the folding behavior of non‐crosslinked ethylene propylene diene terpolymer composites

Conducting Polymer-Coated Carbon Cloth Captures and Releases Extracellular Vesicles by a Rapid and Controlled Redox Process.

Electrochemical techniques offer great opportunities for the capture of chemical and biological entities from complex mixtures and their subsequent release into clean buffers for analysis. Such methods are clean, robust, rapid, and compatible with a wide range of biological fluids. Here, we designed an electrochemically addressable system, based on a conducting terpolymer [P(EDOT-co-EDOTSAc-co-EDOTEG)] coated onto a carbon cloth substrate, to selectively capture and release biological entities using a simple electrochemical redox process. The conducting terpolymer composition was optimized and the terpolymer-coated carbon cloth was extensively characterized using electrochemical analysis, Raman and Fourier transform-infrared spectroscopy, water contact angle analysis, and scanning electron microscopy. The conductive terpolymer possesses a derivative of EDOT with an acetylthiomethyl moiety (EDOTSAc), which is converted into a "free" thiol that then undergoes reversible oxidation/reduction cycles at +1.0 V and -0.8 V (vs Ag/AgCl), respectively. That redox process enables electrochemical capture and on-demand release. We first demonstrated the successful electrochemical capture/release of a fluorescently labeled IgG antibody. The same capture/release procedure was then applied to release extracellular vesicles (EVs), originating from both MCF7 and SKBR3 breast cancer cell line bioreactors. EVs were captured using the substrate-conjugated HER2 antibody which was purified from commercially available trastuzumab. Capture and release of breast cancer EVs using a trastuzumab-derived HER2 antibody has not been reported before (to the best of our knowledge). A rapid (2 min) release at a low potential (-0.8 V) achieved a high release efficiency (>70%) of the captured, HER2+ve, SKBR3 EVs. The developed system and the electrochemical method are efficient and straightforward and have vast potential for the isolation and concentration of various biological targets from large volumes of biological and other (e.g., environmental) samples.

Modulating the nanoscale morphology on carboxylate-pyrazine containing terpolymer toward 17.8% efficiency organic solar cells with enhanced thermal stability

It had been commonly accepted in the organic photovoltaic (OPV) community that subtle variations in the molecular structure of active layer materials would cause profound impacts on their aggregating structure and blend morphology and therefore the performance of such polymer solar cells (PSCs). Herein, we employed an electron-deficient building block 3,6-dithiophenyl-2-carboxylate pyrazine (DTCPz) for constructing one series of promising donor terpolymers of PMZ1, PMZ2, and PMZ3, respectively, gaining their relatively lower-lying highest occupied molecular orbital (HOMO) energy levels, more closed π-π stacking and enhanced crystallinity in thin films, and lower miscibility with acceptor Y6, in comparison with their parent polymer counterpart (namely PM6). Reaching DTCPz moieties up to 20% (mol/mol%) in its terpolymer composition, the resulting polymer (PMZ2) achieved more favorable phase separation with improved exciton dissociation, and charge transport and extraction. As a result, an outstanding fill factor of 77.2% and a promising power conversion efficiency of 17.8 % was achieved. Moreover, the corresponding device shows better thermal stability over the PM6-based one. This work suggests a facile method for significantly improving the thin film morphology of the active-layer materials via fine-tuning the chemical structure of electron-deficient units on the backbone of the wide bandgap donor polymer, therefore achieving enhanced photovoltaic performance and thermal stability for practical applications.

Relationships of the Degree of C=C Double Bond Conversion with the Dielectric Properties for SiO2/1,2‐PB/SBS/EPDM Composites Cured by Organic Peroxide

AbstractPolymer materials with low dielectric constant and dielectric loss play an indispensable role in high speed and stable signal transmission of electronic components. In this work, the SiO2/ 1,2‐polybutadiene/ styrene‐butadiene‐styrene triblock copolymer/ ethylene‐propylene‐diene terpolymer (SiO2/1,2‐PB/SBS/EPDM) composites were prepared with different content of organic peroxide (bis (1‐(tert‐butyl peroxide)‐1‐methyl ethyl)‐benzene, BIPB). A high degree of crosslinking reaction may occur during the curing process. Attenuation total reflectance Fourier transformation infrared spectrometry (ATR‐FTIR) analysis showed that the degree of C=C conversion (DC) increased with the increase of BIPB content, and the dielectric constant of the composites was reduced. However, the dielectric loss decreased initially and subsequently increased. The excess initiators transform into impurities and increase the polarization and conductivity, resulting in a larger dielectric loss value of the composite. The combined results show that the DC value of 92.76 %, the dielectric constant of 3.37 and the dielectric loss of 0.0028 were obtained for the SiO2/1,2‐PB/SBS/EPDM composites containing 3 part‐by‐weight (pbw) BIPB. Furthermore, the composite had good thermal stability and superior mechanical properties.

Hybrid modeling approach for terpolymerization reactions in CSTR

In order to produce terpolymer of desired quality a model capable of simulating terpolymerization is required. Terpolymerization involves complex reactions, full-scale modeling using the frst principle model is not practical to simulate reaction because there are many parameters to be estimated. In this study, a hybrid model that integrates the frst-principles model and the DNN model is proposed. The proposed hybrid model reduces the parameters that need to be estimated using a cumulative composition model, through the steady-state assumption. Afterward, DNN model in a hybrid model estimates the conversion using measurement data from process sensors, and the terpolymer composition according to conversion is calculated. In the process, by estimating model parameters with error in variables model, hybrid model specifc to the system is constructed. Validation of the hybrid model is performed using measurement data of 600 days and the result shows a good agreement with the actual data. The proposed hybrid model has high fdelity, scalability and robustness to other terpolymerization process.

An Eco-Friendly Terpolymer Resin: Synthesis, Characterization and Ion‐Exchange Properties

2, 2’- Biphenol-Hexamethylenediamine-formaldehyde Terpolymers (BPHDF) were synthesized by the condensation of 2, 2’- Biphenol, Hexamethylenediamine, and formaldehyde in the presence of acid catalyst with varying molar ratios of reacting monomers. Terpolymer composition has been determined on the basis of their elemental analysis and the number–average molecular weight of these resins was determined by conductometric titration in nonaqueous medium. The viscosity measurements were carried out in N, N-dimethyl formamide which indicate normal behaviour. IR spectra were studied to elucidate the structure. The terpolymer resin has been further characterized by UV–visible and 1H-NMR spectra. The surface morphology of the terpolymer resin was examined by scanning electron microscopy. One of the important applications of these terpolymers is their capability to act as chelating ion-exchangers. The newly synthesized terpolymers proved to be selective for chelating ion-exchange properties and showed a powerful adsorption towards specific metal ions like Co2+, Hg2+, Cd2+, Pb2+. A batch equilibration method was adopted to study the selectivity of the metal ion uptake involving the measurement of the distribution of the given metal ion between the polymer sample and a solution containing the metal ion over a wide range of concentrations and pHs of different electrolytes. The terpolymers showed a higher selectivity for Co2+> Hg2+> Cd2+> Pb2+.It is also observed that the amount of metal ions absorption by the BPHDF terpolymer resins increases in the order: BPHDF-3 > BPHDF-2 > BPHDF-1 due to introduction of more and more phenolic groups in terpolymer resins from BPHDF-1 to BPHDF-3.

Adhesion Strength of Organic-Inorganic Terpolymers Containing Nanostructured Poly(Titanium Oxide) with Self-Cleaning Properties to Different Materials

Optically transparent organic-inorganic terpolymers based on poly (titanium oxide), hydroxyethyl methacrylate and organic monomers of the vinyl and (meth) acrylic series (acrylonitrile, butyl methacrylate, vinyl butyl ether, 2-ethylhexyl acrylate) were obained as a coating on silicate glass, polycarbonate, touch-up paint and metal. Materials’ light transmittance in the visible spectral range is 87 - 92% depending on the composition. The adhesion of terpolymers’ thin layers to substrates of various natures was investigated under shear deformations and by the lattice notch method according to ISO 15140. It was found that it is necessary to selectively excerpt composition of terpolymers in accordance with the nature of the substrate for creation adhesive durable coatings. The most durable coatings are formed on glass, polycarbonate and automotive enamel. It was revealed that the nature of the substrate and the composition of organic-inorganic terpolymers affect the hydrophobicity of the coatings and their ability to hydrophilize under the influence of UV-irradiation. The contact wetting angle of coatings with water, on average, reversibly varied within ~ 90 ° ↔ ~ 30 °.

Mathematical Modeling of Free Radical Solution Terpolymerization Reactions in a Batch and Continuous Flow Stirred Tank Reactors

AbstractA mathematical model that describes a free radical solution terpolymerization is applied to styrene (St), methyl methacrylate (MMA), and maleic anhydride (MAh) polymerization system. This terpolymerization model allows for the use of either monofunctional or bifunctional peroxide initiators, and it is applied to batch and continuous reactions. The key model outputs are global monomer conversion, terpolymer composition, terpolymer average molecular weights, and terpolymer monomer sequence distributions. A few kinetic parameters are estimated such that global conversion is properly predicted by the model including initiator efficiency and two termination rate constants. Molecular weights are shown to be dominated by chain transfer reactions. Experimental trends of conversion, terpolymer molar masses (molecular weights), and composition are reasonably well predicted by the model.

Effect of nanofillers on the crystalline and mechanical properties of EVACO polymer nanocomposites

In this work, the effect of different fillers on the crystalline and mechanical properties of the poly(ethylene-co-vinyl acetate-co-carbon monoxide) (EVACO) terpolymer composite is studied systematically. Alumina trihydrate nanoparticles (nano-ATH), halloysite nanotubes (HNTs), and the multiwalled carbon nanotubes (MWCNTs) are the representative fillers used in the present study. The surface of MWCNTs are decorated using carbonyl, however, nano-ATH and HNTs are used without any surface treatment. The mechanical properties of the composites are evaluated using a tensile test and the improvement in the mechanical properties can be correlated to the improvement in the crystallinity in the composite. The presence of nanofillers in the EVACO matrix significantly influenced the crystallinity, which was determined by X-ray diffraction. The fractography studies reveal the presence of agglomerates at high filler loading results in the subsequent reduction in the tensile properties. Interestingly, the MWCNTs at very low filler loading significantly enhances the tensile properties of EVACO.