Reactivity Of Double Bond Research Articles

Helical Polyallenes: From Controlled Synthesis to Distinct Properties.

Polyallenes with appropriate pendants can form stable helices and exhibit significant optical activity. These helical polyallenes contain reactive double bonds that allow for further functionalization, making them a class of chiral functional materials with broad application prospects. This review article delves into the intricacies of synthesizing well-defined helical polyallenes through controlled synthetic methodologies, including helix-sense selective living polymerization, regioselective and asymmetric living polymerization, and one-pot block copolymerization of allenes with aryl monomers. The systemically outlined characteristics of the resulting helical polyallenes and related copolymers are summarized include their unique chiroptical properties, stimuli-responsiveness, helix-induced chiral self-assembly, and circularly polarized luminescence (CPL). Additionally, current challenges and future perspectives in the research of controlled synthesis, functionalities, and applications of helical polyallenes are discussed in detail.

Molecular interaction between ammonium sulfate and secondary organic aerosol from styrene

Secondary organic aerosol (SOA) and inorganic aerosol (SIA) are two major constituents of PM2.5, which are well-studied separately. However, the molecular-level investigation of mechanical interactions between them is still limited, which will affect the understanding of toxicity and optical properties of PM2.5. Styrene contains a benzene ring and a highly reactive double bond, mainly contributing to urban SOA formation. Here, chamber experiments were conducted to explore the effects of the (NH4)2SO4 seeds, as an example of SIA, on styrene SOA formation under varying relative humidity (RH) conditions. The particle-phase products were determined based on a high-resolution orbitrap mass spectrometer. The results showed that in the styrene-H2O2-hv systems, (NH4)2SO4 seeds facilitated the gas-particle partitioning of SOA precursors, leading to slightly higher SOA yields than the unseeded systems at 8.5 % RH. While RH exceeded 44.3 %, the presence of (NH4)2SO4 seeds increased the particle liquid water content, thus enhancing the partitioning of hydrophilic H2O2 to particle phase and the further oxidation of SOA, finally decreasing SOA yields. In the styrene-NOx-hv systems, NH4+ and SO42− were involved in the particle-phase reactions, producing prominent nitrogen- and sulfur-containing compounds of C8H7O2N and C8H9O6NS. In the styrene-O3 dark reaction systems, the existence of (NH4)2SO4 seeds significantly changed the oligomer components under humid conditions. The particle-phase formation pathways of oligomers affected by (NH4)2SO4 seeds were also illustrated based on tandem mass spectra data. This study emphasizes the importance of inorganic seed effects on particle-phase reactions and improves our understanding of the SOA formation pathways in the ambient atmosphere.

Triazole‐, piperazine‐, and DOPO‐containing eugenol‐based reactive flame retardant for unsaturated polyester resin

AbstractThe flammability of unsaturated polyester resins (UPRs) limits their applications. Herein, a reactive P‐ and N‐containing flame retardant (DPET) having triazole and piperazine rings is reported. The 9,10‐Dihydro‐9‐oxa‐10‐phosphaphenanthrene 10‐oxide (DOPO) was used to introduce P atoms, and eugenol was used to import reactive double bonds to DPET. Different ratios of DPET were mixed with a commercial UPR and the thermal, mechanical, optical, and flame retardancy properties were measured. The addition of 15% of DPET into neat UPR led to a decrease in the water contact angle from 70° ± 2 to 61° ± 2. The gel content values of the UPRs were found to change between 97.5% and 89%. The optical properties of the UPR were adversely affected by the incorporation of DPET. The modulus of the DPET‐containing UPRs increased with increasing amount of DPET and 15% of DPET‐containing UPR displayed a modulus value of 1784 ± 86 MPa. When 15% DPET was added to neat UPR, char yields were increased (from 5.6% to 16.6%). Limiting oxygen index (LOI) values increased with increasing amounts of DPET and reached up to 23.4%. Micro cone calorimeter (MCC) test results showed up to a 20.5% reduction in the peak heat release rate (PHRR) of the UPR when 15% DPET was added.

Enzyme‐Assisted Activation Technique for Producing Versatile Hydrogel Microparticle Scaffolds with High Surface Chemical Reactivity

AbstractAdvancing the integration of nonliving and living components relies heavily on functional hydrogel materials with biocompatibility and customizability. In this study, an enzyme‐assisted surface activation method is developed to produce reactive hydrogel microparticles (HMPs) comprising thiolated hyaluronic acid and hyperbranched poly(β‐hydrazide esters). Fluorescence labeling analysis reveals an over six‐fold increase in surface‐active functional group density on the hydrogels and three‐fold on HMPs after enzyme activation. This enhancement improves accessibility of active elements, facilitating post‐functionalization and optimizing their capacity to support initial cell adhesion and spreading as carriers for cell cultures. Additionally, by utilizing the exposed reactive double bonds on the HMP surfaces post‐enzymatic treatment, thiolated HMPs are produced through a thiol‐ene coupling reaction with thiolated polymers. These thiolated HMPs bond together spontaneously, resulting in the formation of annealed granular hydrogels with interconnected large‐pore networks and a tunable storage modulus (G’) from tens to hundreds of pascals, compatible with most soft tissues. Integrated with 3D bioprinting, this hydrogel ink generates prints that foster cell adhesion, migration, growth, and network formation. Moving forward, integrating various granular hydrogel scaffold systems with the enzyme‐assisted activation technique holds significant promise for enhancing performance and expanding applications in regenerative medicine and innovative living materials.

From Criegee to Breslow: How π-Donors Steer the Route of Olefin Ozonolysis.

While π-bonds typically undergo cycloaddition with ozone, resulting in the release of much-noticed carbonyl O-oxide Criegee intermediates, lone-pairs of electrons tend to selectively accept a single oxygen atom from O3, producing singlet dioxygen. We questioned whether the introduction of potent electron-donating groups, akin to N-heterocyclic olefins, could influence the reactivity of double bonds - shifting from cycloaddition to oxygen atom transfer or generating lesser-known, yet stabilized, donor-substituted Criegee intermediates. Consequently, we conducted a comparative computational study using density functional theory on a series of model olefins with increasing polarity due to (asymmetric) π-donor substitution. Reaction path computations indicate that highly polarized double bonds, instead of forming primary ozonides in their reaction with O3, exhibit a preference for accepting a single oxygen atom, resulting in a zwitterionic species formally identified as a carbene-carbonyl adduct. This previously unexplored reactivity potentially introduces aldehyde umpolung chemistry (Breslow intermediate) through olefin ozonolysis. Considering solvent effects implicitly reveals that increased solvent polarity further directs the trajectories toward a single oxygen atom transfer reactivity by stabilizing the zwitterionic character of the transition state. The competing modes of chemical reactivity can be explained by a bifurcation of the reaction valley in the post-transition state region.

Biodiesel as a Sustainable Platform Chemical Enabled by Selective Partial Hydrogenation: Compounds Outplace Combustion?!

The hydrogenation of polyunsaturated fatty acids (PUFAs) in vegetable oils and their derivatives is essential for their use in many areas, such as biofuels and food chemistry. However, no attempts have been made to adapt this technology to the requirements of further chemical utilization of fatty acid methyl esters as molecular building blocks, especially for particularly promising double-bond reactions. In this work, we, therefore, use three homogeneous catalytic model reactions (hydroformylation, isomerizing methoxycarbonylation, and ethenolysis) to show, firstly, that it is already known from the literature that high PUFA contents have a negative impact on activity and selectivity. Subsequently, using the example of soybean and canola biodiesel, we demonstrate that these key figures can be drastically improved by a preceding selective partial hydrogenation. This makes it possible to first reduce the share of PUFAs to <1 w % without causing significant overhydrogenation and then to carry out hydroformylation, methoxycarbonylation, and ethenolysis with significantly increased activity (up to twentyfold) and selectivity (up to 80 % increase). With these findings, we hope to convince the scientific and industrial world of the potential of selective partial hydrogenation as a key technology for utilizing renewable raw materials and to encourage its effective use in future work.

Enhancing thermal conductivity and dielectric properties of Al2O3@Si/polyphenylene oxide composites by surface functionalization

Recently, soaring developments in 5 G technology have raised an intensive challenge in developing polymer composites with excellent thermal conductivity and dielectric properties. Herein, Al2O3 @Si/MPPO composites were developed through synergistic modification and solution mixing methods. The double bond reaction between Al2O3 @Si and MPPO enhanced the interfacial force and greatly reduced the interfacial thermal resistance and interfacial polarization, leading to highly thermally conductive composites with excellent dielectric properties. The resultant polymer composites exhibited high thermal stability, excellent dynamic mechanical properties, a low dielectric loss of 0.00292, and a high thermal conductivity (TC) of 1.49 W/(m·K), which was 5.21 times higher than that of the pure MPPO resin, making it an ideal thermal management material for electronic devices.

Reaction kinetic modelling of tar cracking in a non-thermal plasma reactor: Model evaluation and reaction mechanism investigation

Gasification is a process that converts waste into syngas, offering various applications such as fuel, energy, hydrogen production, or further chemicals synthesis. However, tar formation hinders its application due to fouling, corrosion, and catalyst deactivation. Non-thermal plasma (NTP) has emerged as a promising method for tar reforming and cracking, demonstrated through surrogate compounds at the laboratory scale. The scope of this study is to investigate the reaction mechanisms in NTP tar cracking using a zero-dimensional (0D) plasma reactor model with Arrhenius kinetics, aiming to elucidate complex pathways, validate against experimental data, and contribute to the understanding of the reactions. The modelling work utilises a global model to represent NTP. This work collects various reaction kinetics and validates predictions against experimental data. The approach begins with heptane modelling, which is later expanded into (1) toluene in hydrogen gas and (2) a tar mixture (phenol, toluene, and naphthalene) in an oxygen-steam mixture. The model predicts external experimental results with good accuracy, especially at temperatures ranging from 600 to 800 K. The results reveal that radical collisions have a more significant impact on the process than electron impact reactions. Toluene and naphthalene ring-opening reactions occurred when a reactive functional group attacks aromatic double bonds. Finally, the model estimates tar cracking in syngas environment. The low oxygen environment results in secondary tar formation and an abundance of acetylene at the output. Lastly, the assumptions adopted in this study are verified by investigating the impact of plasma and electron temperatures, along with a comparative review of current methodologies in NTP chemistry modelling.

Mechanical Properties, Radiation Resistance Performances, and Mechanism Insights of Nitrile Butadiene Rubber Irradiated with High-Dose Gamma Rays.

The radiation effect of materials is very important and directly related to the safety and reliability of nuclear reactors. Polymer materials, one of the indispensable materials in nuclear power equipment, must withstand the ordeal of high-energy ionizing rays. In this work, through screening different γ-ray dose irradiation conditions, we systematically and comprehensively study the changes in the structure and properties of nitrile butadiene rubber (NBR) before and after γ-ray static irradiation at a high dose rate, and master the rule and mechanism of the γ-ray static irradiation effect of these polymer materials. The mapping relationship between the macroscopic properties, microstructure, and irradiation dose of NBR is accurately characterized. With an increase in total irradiation dose, the C=C double bond reaction occurs, and the C≡N bond, C=C, and C=O participate in the hyper crosslinking reaction. The glass transition temperature (Tg) increases with the cumulative irradiation amount. With the increased total irradiation amount, the degree of rubber cross-linking increases, causing an increased crystallinity and decomposition temperature. A growing amount of gamma irradiation causes the mechanical properties of the rubber to degrade simultaneously, increasing the shore hardness while decreasing the tensile strength and ultimate elongation at break. When the cumulative amount reaches 1 MGy, the ultimate elongation at break decreases significantly. A cumulative dose of radiation resistance of 4 MGy can be achieved by the samples. This work can provide theoretical and experimental support for the long-term stability of nitrile butadiene rubber and its derivatives in nuclear radiation fields and space radiation conditions.

Influence of the molecular structure of phenylamine antioxidants on anti-migration and anti-aging behavior of high-performance nitrile rubber composites

Abstract The structure of antioxidants significantly affects the anti-migration and thermal-oxidative aging properties of nitrile butadiene rubber (NBR) composites, which are crucial for applications in aerospace, biomedical, and fuel cell stack sealing industries. The findings reveal that the migration rate of N-(4-anilino phenyl) maleic imide (MC), with a reactive double bond, is only 15.6%, exhibiting the best extraction resistance. 2,4,6-Tris-(N-1,4-dimethylpentyl-p-phenylenediamino)-1,3,5-triazine (TMPPD), with a greater weight and dendritic structure, follows at 47.7%, while N-isopropyl-N′-phenyl-p-phenylenediamine (4010NA) performs the worst, with 77.8%. Furthermore, after thermal-oxidative exposure, the cross-link density of NBR composites increases, generating oxygenated substances, such as ethers, aldehydes, and acids. The addition of antioxidants in the composites improves the thermal-oxidative aging properties compared to those without any antioxidants. Moreover, antioxidants 4010NA and TMPPD display superior resistance to thermal-oxidative aging properties compared to antioxidant MC.

Enhanced hydrophobic performance of UV-curable palm oil polyurethane by fluoroacrylate monomer

Driven by the versatility of crosslinked complex network formed by the reaction of double bonds during photopolymerization, ultraviolet (UV) curable palm oil polyurethane (POPU) was modified by the addition of fluoroacrylate monomer to increase its hydrophobicity properties. Fourier transform infrared spectroscopy showed a successful attachment of the fluoro group to POPU. Fluoroacrylate palm oil polyurethane (FPOPU) also showed good hydrophobic properties as FPOPU-6% has the highest contact angle which is 108.22°. In the sliding angle test, FPOPU-2% provided the highest roll-off properties with the lowest angle of incline which was 16.6°. The addition of fluoroacrylate at 6% also lowered the water absorption properties of POPU from 4.94% to 3.98%. To further investigate the cause of hydrophobicity increase, scanning electron microscopy and atomic force microscopy analysis were conducted. The morphology showed fluorine component migration increased the roughness of the coating by the coating’s hydrophobicity performance. Overall, fluoroacrylate monomer addition successfully improved the hydrophobic properties of POPU.

Catalytic hydrocracking of pyrolytic lignin in supercritical methanol over nickel‑ruthenium/ceria-deposited HZSM-5

In this study, we explored the catalytic hydrocracking of pyrolytic lignin (PL) under supercritical methanol conditions. This approach aimed to minimize coke formation and prevent solidification of bio-oil, thus improving its manageability and upgrade potential in subsequent steps. Hydrocracking of PL at 250°C for 2 h with HZSM-5, Ni/HZSM-5, and Ni-Ru/HZSM-5 catalysts revealed a dominance of repolymerization over hydrocracking. Consequently, the methanol-soluble oil portion decreased to <37.8 wt%, accompanied by an increase in product molecular weight. However, by co-depositing Ni and Ru on ceria-impregnated HZSM-5 catalysts, the yield of methanol-soluble oil increased to 48.5–56.1 wt%, while the molecular weight decreased. By optimizing reaction parameters using Ni-Ru/Ce-HZSM-5 (NRC4H) at 300°C for 1 h, a methanol-soluble yield of 52.5 wt% was achieved, along with a substantial reduction in molecular weight. The interaction of Ni, Ru, and Ce elements on the catalyst's acidic surface led to smaller Ni and Ru particles and improved reducibility, resulting in a suitable acid-base balance that effectively suppressed repolymerization and enhanced hydrocracking. Furthermore, the detection of methane in the gas product served as an indicator of the hydrogenation reaction of double bonds during the hydrocracking process.

Random and block architectures of N-arylitaconimide monomers with methyl methacrylate

Abstract “Itaconimide” is the members of imide (–CO–NH–CO–) family with reactive exocyclic double bond and it is easily obtained from the renewable resource i.e. D-glucose. The polymerization of various N-arylitaconimide (NAI) monomers with methyl methacrylate (MMA) have been reported to improve the glass transition temperature (T g) and thermal stability of poly(methyl methacrylate) (PMMA). In literature, these studies have been done mostly using conventional free radical polymerization methods, which restricts the architecture of copolymers to “random” only. The block copolymers of NAI and MMA are an important due to the combination of glassy PMMA and thermally stable poly(NAI), which offers its applications for higher temperature service. The architectural control of polymers in provisions of its topology, composition, and various functionalities is possibly obtained using reversible-deactivation radical polymerizations (RDRPs). In RDRPs, the concentration of free radical is controlled in such a way that the termination reactions are minimized (normally in range of 1–10 mol%), and not allowed to obstruct with the desired architecture. However, this is possible by achieving (or by establishing) a rapid dynamic equilibrium between propagating radical and dormant species (i.e. R–X). Among all RDRPs, the atom transfer radical polymerization (ATRP) is very popular and adaptable method for the synthesis of polymers with specifically controlled architecture. Two different architectures of NAI and MMA copolymers are reported using ATRP process. The effect of various pedant groups on the rate constants of propagation (k p) and thermal properties NAI and MMA copolymers is studied. The poly(NAI-ran-MMA)-b-poly(MMA) are stable up to 200 °C and degraded in three steps. Whereas, the poly(NAI-ran-MMA)-b-poly(NAI) are stable up to 330 °C and degraded in two steps. The density functional theory methods are used for calculation of equilibrium constants (K ATRP) for the ATRP process for the series of laboratory synthesized alkyl halides. A good agreement was observed between the experimentally determined and theoretically calculated K ATRP values. The mechanistic studies are carried for poly(NAI-ran-MMA) copolymer system using statistical model discrimination method along with 1H decoupled 13C NMR spectroscopy. For studying the mechanism of copolymerization of NAI and MMA via ATRP methods, “trimer model or penultimate model” will be more accurate than “dimer model or terminal model”.

In‐situ formation of macromolecule P/N/Si flame retardant for epoxy resin with low smoke toxicity and excellent flame‐retardancy

AbstractEpoxy resins (EP) have great chemical and physical properties, but their poor flame retardant properties have prevented their widespread use. To improve the flame retardancy properties of EP, an active P/N/Si flame retardant (KDC) containing a double bond was successfully synthesized in this work by using a typical aldehyde amine condensation reaction. This flame retardant not only can form a large molecule flame retardant in situ by double bond reaction and increase the tightness with EP matrix, but also has the advantage of P/N/Si three elements synergistic flame retardant, and at the same time play the flame retardant performance of each element, can achieve excellent flame retardant performance and low smoke and toxicity with low addition amount. Subsequently, the performance of the flame retardants was tested. When 7 wt% of KDC was added, the pHRR and TSR of the EP composites were reduced by 51.7% and 29.8%, respectively. More importantly, the addition of KDC inhibited the release of toxic fuels and smoke from EP, where the TSP values of EP/3‐KDC were 18.14% below those of neat EP and increased the residual amount of charcoal, while the inhibition of CO and CO2 release was particularly pronounced with the presence of KDC.

A versatile modification strategy for functional non-glutaraldehyde cross-linked bioprosthetic heart valves with enhanced anticoagulant, anticalcification and endothelialization properties.

Valvular heart disease is a major threat to human health and transcatheter heart valve replacement (THVR) has emerged as the primary treatment option for severe heart valve disease. Bioprosthetic heart valves (BHVs) with superior hemodynamic performance and compressibility have become the first choice for THVR, and more BHVs have been requested for clinical use in recent years. However, several drawbacks remain for the commercial BHVs cross-linked by glutaraldehyde, including calcification, thrombin, poor biocompatibility and difficulty in endothelialization, which would further reduce the BHVs' lifetime. This study developed a dual-functional non-glutaraldehyde crosslinking reagent OX-VI, which can provide BHV materials with reactive double bonds (CC) for further bio-function modification in addition to the crosslinking function. BHV material PBAF@OX-PP was developed from OX-VI treated porcine pericardium (PP) after the polymerization with 4-vinylbenzene boronic acid and the subsequent modification of poly (vinyl alcohol) and fucoidan. Based on the functional anti-coagulation and endothelialization strategy and dual-functional crosslinking reagent, PBAF@OX-PP has better anti-coagulation and anti-calcification properties, higher biocompatibility, and improved endothelial cells proliferation when compared to Glut-treated PP, as well as the satisfactory mechanical properties and enhanced resistance effect to enzymatic degradation, making it a promising candidate in the clinical application of BHVs. STATEMENT OF SIGNIFICANCE: Transcatheter heart valve replacement (THVR) has become the main solution for severe valvular heart disease. However, bioprosthetic heart valves (BHVs) used in THVR exhibit fatal drawbacks such as calcification, thrombin and difficulty for endothelialization, which are due to the glutaraldehyde crosslinking, resulting in a limited lifetime to 10-15 years. A new non-glutaraldehyde cross-linker OX-VI has been designed, which can not only show great crosslinking ability but also offer the BHVs with reactive double bonds (CC) for further bio-function modification. Based on the dual-functional crosslinking reagent OX-VI, a versatile modification strategy was developed and the BHV material (PBAF@OX-PP) has been developed and shows significantly enhanced anticoagulant, anti-calcification and endothelialization properties, making it a promising candidate in the clinical application of BHVs.

Activation of the Keap1/Nrf2 Pathway as an Adaptive Response to an Electrophilic Metabolite of Morphine.

Morphinone (MO) is an electrophilic metabolite of morphine that covalently binds to protein thiols via its α,β-unsaturated carbonyl group, resulting in toxicity in vitro and in vivo. Our previous studies identified a variety of redox signaling pathways that are activated during electrophilic stress. Here, we examined in vitro activation of a signaling pathway involving Kelch-like ECH-associated protein 1 (Keap1) and nuclear factor erythroid 2-related factor 2 (Nrf2) in response to MO. Exposure of HepG2 cells to MO caused covalent modification of Keap1 thiols (evaluated using biotin-PEAC5-maleimide labeling) and nuclear translocation of Nrf2, thereby up-regulating downstream genes encoding ATP binding cassette subfamily C member 2, solute carrier family 7 member 11, glutamate-cysteine ligase catalytic subunit, glutamate-cysteine ligase modifier subunit, glutathione S-transferase alpha 1, and heme oxygenase 1. However, dihydromorphinone, a metabolite of morphine lacking the reactive C7-C8 double bond, had little effect on Nrf2 activation. These results suggest that covalent modification is crucial in the Keap1/Nrf2 pathway activation and that this pathway is a redox signaling-associated adaptive response to MO metabolism.

N-acetyl cysteine inhibits IL-1α release from murine keratinocytes induced by 2-hydroxyethyl methacrylate.

The hydrophilic compound 2-hydroxyethyl methacrylate (HEMA) is a major component of dental bonding materials, and it enhances the binding of resin-composites to biomolecules. However, HEMA is a well-known contact sensitizer. We reported previously that intradermal injection of HEMA induces the production of IL-1 locally in the skin. Keratinocytes are the first barrier against chemical insults and constitutively express IL-1α. In this study, we analyzed whether HEMA induces the production of inflammatory cytokines from murine keratinocyte cell line Pam212 cells. We demonstrated that HEMA induced the release of 17-kDa mature IL-1α and caused cytotoxicity. The activity of calpain, an IL-1α processing enzyme, was significantly higher in HEMA-treated cells. The thiol-containing antioxidant N-acetyl cysteine (NAC) inhibited HEMA-induced IL-1α release but not cytotoxicity. NAC inhibited intracellular calpain activity and reactive oxygen species (ROS) production induced by HEMA. NAC post-treatment also inhibited IL-1α release and intracellular ROS production induced by HEMA. Furthermore, HEMA-induced in vivo inflammation also inhibited by NAC. NAC inhibited polymerization of HEMA through adduct formation via sulfide bonds between the thiol group of NAC and the reactive double bond of HEMA. HEMA-induced IL-1α release and cytotoxicity were also inhibited if HEMA and NAC were pre-incubated before adding to the cells. These results suggested that NAC inhibited IL-1α release through decreases in intracellular ROS and the adduct formation with HEMA. We concluded that HEMA induces IL-1α release from skin keratinocytes, and NAC may be a promising candidate as a therapeutic agent against inflammation induced by HEMA.

Исследование относительной реакционной способности паров алкилацетатов по отношению к компонентам плазмы импульсного разряда в воздухе

A study was made of the relative reactivity of vapors of a number of acetic acid esters (alkyl acetates) with respect to plasma components of a pulsed corona discharge with a voltage of 100 kV and a duration of 40 ns. On model mixtures based on methyl-, ethyl-, propyl-, isopropyl, isobutyl-, butyl-, and vinyl acetate with a content of 250–500 ppm in air and nitrogen, the relative reactivity parameters were obtained. The reactivity of acetic acid esters increases with an increase in the hydrocarbon substituent. The high reactivity of vinyl acetate is due to the double bond reaction with ozone.

Synthesis of green thermo-responsive amphoteric terpolymer functionalized silica nanocomposite derived from waste vegetable oil triglycerides for enhanced oil recovery (EOR)

Despite the high efficiency of polymer flooding as a chemical enhanced oil recovery (CEOR) technique, the low thermal stability and poor salt resistance of widely applied partially hydrolyzed polyacrylamide (HPAM) limited the application of this technique in oil reservoirs at harsh reservoir conditions of high–temperature and high–salinity (HTHS). These inadequacies of HPAM, result in the urge for an environmentally friendly polymer with good viscosifying properties and a substantial effect on mobility ratio at HTHS reservoir conditions. In this research, a high oleic acid waste vegetable oil (WVO) is utilized to synthesize a novel environmentally benign, thermo-responsive amphoteric nanocomposite for EOR applications at HTHS reservoir conditions. A green route transesterification reaction has been utilized to synthesize a novel thermo-sensitive monomer from WVO. The existence of unsaturated fatty acids isolated double bonds and acryloyl functional groups in the synthesized monomer has been confirmed using different characterization methods. The reactive acryloyl double bond in the synthesized monomer has been copolymerized with acrylamide, acrylacyloxyethyltrimethyl ammonium chloride, and 2-acrylamide-2-methylpropane sulfonic acid in presence of dimethylphenylvinylsilane via free radical emulsion polymerization. The synthesized nanocomposite has been characterized by FTIR, 1H NMR, SEM, EDX, TEM, and DLS. The thermal stability of the nanocomposite has been evaluated by TGA and DTA analysis. The results indicated that nanocomposite solution exhibited a pouncing thermo-thickening behaviour and superior viscosifying properties even at an ultra-low polymer concentration of 0.04 wt% as the temperature increased from 25 to 100 °C, with increasing salinity from 10,000 to 230,000 ppm as well as salt-free solutions. Flooding experiments demonstrated that the oil recovery factor reached 15.4 ± 0.1 % using low nanocomposite concentrations of 0.04 wt%, 22.6 ± 0.3 % using nanocomposite concentrations of 0.06 wt% and 25 ± 0.2 % using 0.1 wt% nanocomposite concentrations evaluated under hostile conditions of 100 °C and salinity of about 230,000 ppm. This research offers a new direction for the synthesis of a novel green, high molecular weight thermoresponsive nanocomposite for EOR application at extremely harsh reservoir conditions via WVO valorization.

Activated polyallene as versatile substrate for efficient preparation of fluorinated composite

Introduction of fluorine into composites has been a subject of intense research because it brings about significant improvements in the performance of the composites. In particular, fluorine-containing composites exhibit excellent thermal stability, good chemical stability and low surface energy. However, the design of fluorine-containing composites is limited by the current polymerization and modification techniques. Herein, a series of double-bond-containing poly(phenoxyallene) (PPOA) polymers with tunable structure were facilely prepared through reversible addition-fragmentation chain transfer (RAFT) polymerization. To identify the RAFT polymerization conditions, RAFT homopolymerization of phenoxyallene (POA) was firstly conducted as a typical reaction. The effects of chain transfer agent (CTA), substituent of POA, temperature, and solvent were systematically investigated. Notably, highly efficient thiol-ene click reaction can be used for the direct modification of PPOA without further polymeric functionality transformation. When fluorinated thiol was used as reactant, a functional fluorine-containing polymer could be simply achieved, demonstrating the highly efficient efficiency of the postpolymerization modification. Considering the simple RAFT polymerization condition and excellent reactivity of double bonds in polymer structure, this thiol-ene postpolymerization modification might be a versatile platform for the precise fabrication of a broad variety of functional composites, especially for fluorine-containing composites.