Quaternary Polymer Research Articles

Preparation and properties of silicone modified BA/MMA/VAc/VeoVa10 quaternary polymer latex

Preparation and properties of silicone modified BA/MMA/VAc/VeoVa10 quaternary polymer latex

Synthesis and evaluation of a new scale inhibitor: the modified epoxysuccinic acid copolymer

Polyepoxysuccinic acid (PESA) scale inhibitor is widely recognized as a green and environmentally friendly scale inhibitor. However, its functional group type is single and cannot be used for a variety of scales. Based on this, a modified epoxy succinic acid quaternary polymer scale inhibitor PEAPS was prepared by introducing a variety of functional groups. The effects of scale inhibitor dosage, temperature, and solution pH on the scale inhibition performance of CaCO3, CaSO4, BaSO4, and SrSO4 were studied. At the same time, it is compared with the commonly used oilfield scale inhibitors Polyacrylic acid (PAA), PESA, and Ethylenediaminetetramethylenephosphonic acid (EDTMP). The results show that under the optimal synthesis conditions, the scale inhibition efficiency of PEAPS scale inhibitor on CaCO3 scale and CaSO4 reaches 100%, and the scale inhibition efficiency of BaSO4 and SrSO4 can reach at least 60%. Its comprehensive scale inhibition efficiency is better than other commonly used scale inhibitors under the same test conditions, and it has certain corrosion inhibition performance through static corrosion evaluation. The crystal parameters and micro-morphology of the four scales before and after the addition of scale inhibitor were analyzed using SEM and XRD. The results showed that after adding the PEAPS scale inhibitor, the crystal structure parameters of the CaCO3 scale and CaSO4 scale changed, and the micro-morphology of the four scale crystals also changed, to achieve the purpose of scale inhibition.

A novel low molecular quaternary polymer as shale hydration inhibitor

Polymer inhibitors for deep shale gas drilling have poor temperature resistance and can influence the rheological attributes of the drilling muds. To overcome this issue, a high temperature resistant and low molecular weight quaternary polymer DVAA was prepared by hydrothermal radical polymerization. The characterizations of the DVAA were evaluated by IR, NMR, TG, and GPC, and the inhibition, rheology, and filtration parameters were examined. The shale inhibition mechanism was evaluated by the SEM, zeta potential, contact angle, and XRD. Initial decomposition temperature of DVAA is 354.83 °C and Mp is 4583. The performance test outcomes suggest that using DVAA could lead to a linear expansion reduction rate of MMT at 73.4%, whereas the rolling recovery rate of cuttings was 86.25%. The API filtration of 4% MMT after hot-rolling is 13.6 ml. The mechanism of DVAA showed that DVAA and MMT form ionic bonds and hydrogen bond through electrostatic attraction and can still maintain a good structure under elevated temperature conditions. DVAA can effectively weaken the surface hydration by entering the crystal layer to replace the inter-layer cations, where it forms a polymer-film on the bentonite surface. In summary, the research and development of the DVAA can provide an effective guarantee for the stability of the wellbore during the development of deep shale gas reservoirs.

Dynamic multi-level microstructured antifouling surfaces by combining quaternary ammonium modified GO with self-polishing copolymers

Marine biological fouling is the undesirable accumulation on the surfaces of submerged objects and causes environmental and economic consequence to ships and marine facilities. However, traditional coatings achieve antifouling by releasing toxic heavy metal antifouling agents, causing ecological problems. And the static antifouling performance of self-polishing antifouling coating is not good. To overcome the shortcoming, a novel antifouling strategy to build a self-renewing multi-level microstructure on the coating surface was developed by dispersing GO-based quaternary polymer brushes in a self-polishing fluoro/silyl acrylate copolymer. Quaternized GO exhibits excellent dispersibility in the silyl-based acrylate copolymer. A dynamic self-renewing surface is realized for the coating via a self-polishing effect that exposes the filler inside the coating at the surface. The multi-level microstructure of the sharp edge of GO and quaternized “spear” structure destroys the cell wall of organisms. And a “water-shield” on amphoteric ion surface on quaternized GO inhibits adhesion of organisms. The antibacterial and anti-algae tests demonstrated the excellent antifouling effect of the coating at only 0.1% (mass) filler content, with anti-algae ratio against Nitzschia closterium (N. closterium), Phaeodactylum tricornutum (P. tricornutum) and Halamphora sp. of 83.7%, 52.4%, and 65.8%, respectively. The proposed preparation method is simple and potentially applicable to large-scale production for antifouling application.

Fabrication of binary to quaternary PVDF based flexible composite films and ultrathin sandwich structured quaternary PVDF/CB/g-C3N4/BaFe11.5Al0.5O19 composite films for efficient EMI shielding performance

This work reports the facile fabrication of binary, ternary, and quaternary polymer composite films using combinations of Polyvinylidene fluoride (PVDF), Carbon Black (CB), Graphitic carbon nitride (g-C3N4), and Aluminum doped Barium hexaferrite (BaFe11.5Al0.5O19) nanoplatelets for application as EMI shielding materials at X-band frequency. The excellent total EMI-SE of 47.39 dB in X-band for ultra-small thickness of 0.193 mm was observed for the quaternary PVDF/CB/g-C3N4/BaFe11.5Al0.5O19 composite film. The quaternary composite film was further hot pressed into sandwich-structured two-layer and three-layer composite films. The sandwich and/or multi-layered structure of the PVDF/CB/g-C3N4/BaFe11.5Al0.5O19 composite film improved the EMI shielding performance through multiple reflection loss. With the addition of intact conduction of fillers and multiple-reflection-absorption effect, the multi-layered composite structure attained the best shielding efficiency (SE) of 64.54 dB.

High-performance quaternary polymer solid-state electrolyte via one-step casting method

Lithium-ion batteries have achieved huge success in the field of energy storage, but they use flammable electrolytes that may cause safety issue. Solid polymer electrolytes have been considered as the final solution to this safety issue, which have received many researchers’ attention. However, solid polymer electrolytes still face several challenges, such as low ionic conductivity. Herein, we report a quaternary solid polymer electrolyte to achieve high ionic conductivity, which was synthesized by one-step casting method. This quaternary electrolyte contains two polymers (poly(vinylidene fluoride-co-hexafluoropropylene) and poly(ethylene oxide) diacrylate), one plasticizer (succinonitrile), and one lithium salt (lithium bis(trifluoromethane)sulfonimide). Long-chain polymer is used as matrix, and short-chain polymer and plasticizer are used to increase ionic conductivity. This quaternary electrolyte achieves a high ionic conductivity of 1.49 × 10−4 S cm−1 at room temperature. When assembled into coin cell with lithium iron phosphate cathode and lithium metal anode, this quaternary electrolyte achieves a capacity of 139 mAh g−1 at 0.2 C after 50 cycles and 106 mAh g−1 at 1 C after 160 cycles. Moreover, this facile one-step casting method provides a new route towards the development of solid polymer electrolytes.

Reducing Limitations of Aggregation‐Induced Photocarrier Trapping for Photovoltaic Stability via Tailoring Intermolecular Electron–Phonon Coupling in Highly Efficient Quaternary Polymer Solar Cells (Adv. Energy Mater. 6/2022)

Organic Solar Cells In article number 2103371, Xiao-Yan Du, Xiao-Tao Hao and co-workers rationalize the underlying correlation mechanisms between intermolecular electron-phonon coupling and trapping of electronic excitation behind the kinetic aggregation behaviors of BTP-eC9 in bulk-heterojunction and layer-by-layer processed multicomponent organic solar cells.

Reducing Limitations of Aggregation‐Induced Photocarrier Trapping for Photovoltaic Stability via Tailoring Intermolecular Electron–Phonon Coupling in Highly Efficient Quaternary Polymer Solar Cells

AbstractThe kinetic aggregation of nonfullerene acceptors under nonequilibrium conditions can induce electron–phonon interaction roll‐off and electronic band structure transition, which represents an important limitation for long‐term operational stability of organic solar cells (OSCs). However, the fundamental underlying mechanisms have received limited attention. Herein, a photophysical correlation picture between intermolecular electron–phonon coupling and trapping of electronic excitation is proposed based on the different aggregation behaviors of BTP‐eC9 in bulk‐heterojunction and layer‐by‐layer processed multicomponent OSCs. Two separate factors rationalize their correlation mechanisms: 1) the local lattice and/or molecular deformation can be regarded as the results of BTP‐eC9 aggregates in binary system under continuous heating, which brings about attenuated intermolecular electron–phonon coupling with intensified photocarrier trapping. 2) The higher density of trap states with more extended tails into the bandgap give rise to the formation of highly localized trapped polarons with a longer lifetime. The stabilized intermolecular electron–phonon coupling through synergistic regulation of donor and acceptor materials effectively suppresses unfavorable photocarrier trapping, delivering the improved device efficiency of 18.10% and enhanced thermal stability in quaternary OSCs. These results provide valuable property–function insights for further boosting photovoltaic stability in view of modulating intermolecular electron–phonon coupling.

Post‐extrusion process for the robust preparation of highly uniform multiphase polymeric 3D printing filaments

AbstractFused filament fabrication 3D printing demands the preparation of polymeric filaments of highly uniform dimensions in order to achieve the best possible mechanical performance. This stringent requirement is a challenging task and becomes even more difficult when multiphase hybrid polymers are used. In this work, a post‐extrusion setup is presented, allowing for the preparation of immiscible quaternary polymeric blend filaments of highly stable dimensions. The polymer blend used is bio‐based and is comprised of poly(L‐lactide), poly(ethylene oxide), poly(ether‐b‐amide), and polyamide‐11. The setup is connected to an extruder die. By incorporating a precisely localized temperature control over a pathway of 66 mm, the extrudate melt is initially transformed into a stable semisolid state. Forced convection cooling, imposed at a distance of 4–5 mm from the last static cooling zone, allows thereafter the complete solidification of the profile. Filaments with a uniform diameter of 1.75 and 2.85 mm are manufactured. The developed approach can be used to manufacture, otherwise non‐processable, complex quaternary polymer blend filaments with a highly controlled diameter in the range of 0.1–4.5 mm with no restriction regarding the filament length. The produced filaments were used to 3D print dogbone samples with very high elongation at break.

Experimental Study on High-Performers Quaternary Copolymer Based on Host-Guest Effect.

A quaternary polymer (HGP) was prepared by the free-radical polymerization of acrylamide, acrylic acid, maleic anhydride functionalized β-cyclodextrin (MAH-β-CD), and N-(3-methacrylamidopropyl)-N, N-dimethylnaphthalen-1-aminium chloride (NAP). It was found that host–guest behavior occurred most effectively at a molar rate of NAP and CD with 1:1, which exhibited better solubility than hydrophobically associative polymer. Moreover, the as-prepared polymer has superior salt tolerance, shear resistance, and viscoelasticity due to host–guest strategy. More importantly, the HGP solution simulates the distribution of formation water in the Bohai SZ1-1 oilfield has good rheological properties at 120 °C. All results show that the proposed polymer could be a competitive candidate in oilfield applications such as fracturing fluids, displacement fluids, and drilling fluids.

High Performance Hydrophobic Associated Polymer for Fracturing Fluids with Low-Dosage

Hydrophobic associated polymer is widely used as fracturing fluids, but its cost is often higher than natural polymers. In order to reduce the cost, quaternary polymer AM/AA/NVP/MAO-12DAM (AANM) was successfully synthesized. The incorporation of N-vinyl-2-pyrrolidone (NVP) improves the temperature resistance of the polymer solution. Rheological and viscoelasticity test results showed that fluids with a lower dosage of AANM in the absence of any crosslinker had better performances than Guar gum (GG) with a crosslinker. Therefore, AANM is expected to be a more economical fracturing fluid thickener than GG.

Gradient Functionalization of Various Quaternized Polyethylenimines on Microfluidic Chips for the Rapid Appraisal of Antibacterial Potencies.

The ability to appraise antibacterial potencies of surface-immobilized bactericidal polymers is still a major challenge in the engineering of antibacterial surfaces to combat hospital-acquired (nosocomial) infections. In this work, we fabricated a microfluidic platform with gradiently immobilized bactericidal polymers to enable the rapid appraisal of antibacterial potencies by in situ live/dead staining of bacteria. To this end, a variety of synthetic quaternary polymers, named QPEI-C1, QPEI-C6, QPEI-C8, and QPEI-C10, were gradiently immobilized in microfluidic channels, and their surface densities at different distances along the channels were quantified by using fluorescein-labeled polymers. We found that the surface densities of quaternary polymers could be well-tuned, and the length of the channel, resulting in a 50% reduction of live bacteria (L50), can be used to appraise the antibacterial potency of each bactericidal polymer. For instance, the L50 values of QPEI-C6-, QPEI-C8-, and QPEI-C10-modified channels against Escherichia coli were 35.5, 44.7, and 49.2 mm, respectively, indicating that QPEI-C10 exerted the most potent antibacterial efficacy. More importantly, this microfluidic platform enabled the rapid discrimination of antibacterial potencies of polymers (e.g., QPEI-C8, and QPEI-C10) while the conventional live/dead staining method found no significant difference. This work provides a powerful toolkit by combining advances of microfluidic systems and polymer science for the rapid screening of antibacterial coatings, which would find applications in surface modification of medical devices to combat bacterial infections.

Constructing the core–shell structured island domain in polymer blends to achieve high dielectric constant and low loss

AbstractCarbon nanotubes (CNTs) and barium titanate (BaTiO3) (BT) were simultaneously introduced into the immiscible blend poly(ethylene‐co‐vinyl acetate)/thermoplastic urethane (EVA/TPU), and the EVA/TPU/CNT/BT quaternary polymer composite blends with core–shell structured island TPU domain were successfully prepared, in which CNTs in the TPU domain act as the core and the BT spheres at the interface of the TPU and EVA act as the shell. A core–shell structured island can lead to the formation of micro‐capacitors and further accumulate electron storage owing to the incorporation of CNTs and BT; on the other hand, a BT shell can be assembled along the TPU spheres, reducing the possibility of formation of a conductive CNT network, resulting in suppressed dielectric loss. Therefore, CNTs and BT were tailor‐made into blend composites with a core–shell structured domain, which can achieve an increased dielectric constant by 176% and decreased low dielectric loss by 80% compared with the blend composites with only CNTs in the TPU domain. © 2019 Society of Chemical Industry

Preparation of a Novel Fracturing Fluid System with Excellent Elasticity and Low Friction.

The quaternary polymer was synthesized by radical polymerization and characterized by 1H NMR. The tests of critical associating concentration and SEM suggest that there is a multilayered and robust network structure in the polymer solution. An excellent elasticity in the polymer solution by the first normal stress difference, viscoelasticity, and thixotropy was observed. The critical crosslinker concentration of polymer with sodium dodecyl sulfate and its interaction mechanism were investigated. According to the reaction kinetics, the supramolecular structure had the lowest activation energy, stable network structure, and greater thermal stability. Then the polymer was employed in the fracturing fluid due to its excellent elasticity using the intermolecular forces, which showed superior sand suspension capacity by dynamic sand suspension measurement. Meanwhile, a theoretical analysis was proposed as to why polymer solution has excellent suspension and drag reduction properties. Therefore, this polymer could be an alternative in many fields, especially in fracking, which is significant for the development of oil and gas resources in deep wells.

Quaternary polymeric coatings as alternative to minimize the use of single solvent: Poly(methyl methacrylate) – ethylbenzene – toluene – acetone system

A gravimetric study of a quaternary polymer system of the poly(methyl methacrylate)-ethylbenzene-toluene-acetone coatings has been carried out. The effects of the coating parameters, namely, initial thickness and coating composition have been studied. The evolution of the residual solvent, average concentrations of polymers and solvents, and coating thickness of the quaternary coating system have been compared with that of the binary and ternary coatings. The results indicate that the amount of any toxic or costly solvents can be reduced to a significant extent in quaternary coatings.

Quaternary polymer solar cells with over 13% efficiency enabled by improving film-morphologiesviabinary mixed fullerene additive

The use of binary mixed fullerene additive outperforms the use of single fullerene additive.

From binary to quaternary: high-tolerance of multi-acceptors enables development of efficient polymer solar cells

Two typical fullerene derivatives were incorporated into a PTB7-Th:IEICO-4F binary host to enable development of efficient quaternary polymer solar cells with PCE values up to 12.52%.

13%-Efficiency Quaternary Polymer Solar Cell with Nonfullerene and Fullerene as Mixed Electron Acceptor Materials.

In this article, we report 13%-efficiency quaternary polymer solar cell. By introducing bis-PC71BM:PC71BM into a known nonfullerene system-poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl))benzo[1,2- b:4,5- b']dithiophene)- co-(1,3-di(5-thiophene-2-yl)-5,7-bis(2-ethylhexyl)benzo[1,2- c:4,5- c']dithiophene-4,8-dione):3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone-methyl))-5,5,11,11-tetrakis(4- n-hexylphenyl)-dithieno[2,3 d:2',3' d']- s-indaceno[1,2 b:5,6 b']dithiophene (PBDB-T:IT-M), the quaternary solar cell significantly outperforms the nonfullerene binary and the ternary (PBDB-T:IT-M:fullerene) devices with a significant increase in the short-circuit current-density (18.2 vs 16.5 and 16.8-17.5 mA/cm2) and the fill factor (0.73 vs 0.67 and 0.707-0.726), and hence, large power conversion efficiency (13% for quaternary vs 11% for the binary and 12% for the ternary). Grazing incidence wide-angle X-ray scattering data indicate that both the polymer and IT-M phase crystallinity becomes greater upon introduction of PC71BM as the forth additive into the host ternary PBDB-T:IT-M:bis-PC71BM, which results in an increase in both the electron and hole mobilities, contributing to the Jsc enhancement. Our results indicate that the use of the forth fullerene component provides more choices and more mechanisms than the ternary systems for tuning the photon-to-electron conversion; therefore, sheds light on the realization of high-efficiency polymer solar cells by designing the multiacceptor components with aligned energy levels, complementary absorption spectra, and improved film morphologies.

High-efficiency quaternary polymer solar cells enabled with binary fullerene additives to reduce nonfullerene acceptor optical band gap and improve carriers transport

The polymer/small-molecule electron donor and nonfullerene organic electron acceptor are of structural similarity with both donor and acceptor molecules consisting of polycyclic fused-ring backbone and being decorated with alkyl-chains. In this study, we report that the introduction of binary fullerenes (C60-/C70-PCBM and C60-/C70-ICBA) into a nonfullerene binary system PBDB-T:ITIC reduces the polymer-nonfullerene acceptor intermixing, obtaining higher crystallinity with (100) crystal coherence length from 28 to 29–33 nm for the ITIC, and from 14 to 20–24 nm for the PBDB-T, and improved electron and hole mobilities both. Unprecedentedly, such a protocol reduces the ITIC optical band gap from 1.59 to 1.55 eV. As consequences, higher short-circuit current-density (17.8–18.4 vs. 15.8 mA/cm2), open-circuit voltage (0.92 vs. 0.90 V) and fill-factor (0.72–0.73 vs. 0.68) are simultaneously obtained, which ultimately afford higher efficient quaternary polymer solar cells with power conversion efficiencies (PCEs) up to 12.0%–12.8% comparing to the host binary device with 9.9% efficiency. For the polymer, ITIC, and ICBA/PCBM ternary blends, 11% PCEs were recorded. The use of PCBM leads to larger red-shifting in thin film absorption and external quantum efficiency (EQE) response. Such effect is more pronounced when ICBA:PCBM mixture is used. These results indicate the size and shape of C60 and C70 as well as the substituent position of the second indene unit on C60-/C70-ICBA affect not only the blend morphology but also the electronic coupling in BHJ mixtures: the quaternary device performance increased in sequences of C70-PCBM:C70-ICBA ® C70-PCBM:C60-ICBA ® C60-PCBM:C70-ICBA ® C60-PCBM:C60-ICBA. The resonant soft X-ray scattering (RSoXS) data indicated the most refined phase separation in the C60-PCBM:C60-ICBA based blend, corresponding to its best device function among the quaternary devices. These results indicate that the using of binary fullerenes as the acceptor additives allows for tuning nonfullerene blended film’s optical properties and film-morphologies, shedding light on the designing high-performance multi-acceptor polymer solar cells.

Effect of basalt, silica sand and fly ash on the mechanical properties of quaternary polymer concretes

The aim of this study is to manufacture quaternary polymer concretes (PCs) and optimize the weight percentages of the epoxy resin, ultrafine fly ash, silica sand and basalt aggregates. For this, we first manufactured binary PCs of epoxy/basalt, epoxy/silica sand and epoxy/fly ash and then studied the mechanical properties such as compressive, flexural and splitting tensile strength. The mixture design method was used as an approach for design of experiment to reduce the number of tests and optimize the mechanical strength of the PC. The best weight percentages of the PC components were 25 (epoxy), 5 (fly ash), 52.5 (silica sand) and 17.5 (basalt). The compressive, flexural and splitting tensile strength of the quaternary PC were equal to 94.1, 39.0 and 11.8, which were 3.76, 11.1 and 6.5 times higher than those of ordinary Portland cement, respectively. Finally, a scanning electron microscopy test was implemented to study the microstructure of the PC.