Vinylimidazole‐based asymmetric ion pair comonomers: Synthesis,polymerization studies and formation of ionically crosslinked PMMA

Vinylimidazole‐based asymmetric ion pair comonomers ( IPC s) which are free from nonpolymerizable counter ions have been synthesized, characterized and polymerized by free radical polymerization (FRP), atom transfer radical polymerization (ATRP), and reversible addition‐fragmentation chain transfer (RAFT) mediated polymerizations in solution and by dispersion polymerization in water. The asymmetric nature of IPC s is due to the fact that cationic component of these IPCs is derived from vinylimidazole (VIm) and anionic component is derived from either styrenesulfonate (SS) or 2‐acrylamido‐2‐methyl‐1‐propanesulfonate. Although under ATRP, conversions are either very low or negligible, FRP and RAFT produces polymers with high to moderate monomer conversions but with different solubility characteristics. This investigation provides insight to the polymerization behavior of each component of the asymmetric IPCs and also its effects on composition and solubility characteristics of the resulting polymers. The IPCs studied here are high temperature ionic liquid and thus the polymers synthesized from these IPCs are highly ionic in nature and possess very strong intermolecular interactions which makes some of these IPC based polymers completely insoluble in organic and aqueous solvents. This highly ionic interaction is exploited to synthesize ionically crosslinked PMMA. MMA on copolymerization with 5–6 mol % of IPC yielded copolymer which is insoluble in common organic solvents like THF, DMF, etc., unlike homo PMMA. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3260–3273     

Rapid identification of trimethyl and triethyl amines using sulphonic acidic ionic liquids: A time-of-flight secondary ion mass spectrometry study of fragmentation reactions

The time-of-flight secondary ion mass spectrometry (TOF-SIMS) has emerged as a powerful tool for the unswerving detection of biomolecules, in particular, proteins and peptides. To date, there is very little information available on the direct determination of trimethyl/triethyl amines using TOF-SIMS. One major hurdle in this regard is an ultrahigh vacuum system, usually needed in TOF-SIMS, which hampers its usability to trimethyl/triethyl amines owing to their high evaporation rate. We designed an efficient and sensitive protocol for rapid identification and sensitive determination of tertiaryalkyl amines using TOF-SIMS. The amines were derivatized by reaction with 1,4-butane sultone and sulphuric acid sequentially to afford the corresponding sulphonic acidic ionic liquids (ILs). The TOF-SIMS analysis of these task-specific ILs (TSILs) was carried out in both positive and negative polarity. The positive ion mass spectra of TSILs showed sharp fragmented peaks for tertiaryalkyl amines at typical level and up to 10 ppm. The possible mechanism for different fragmentation pathways in positive polarity was discussed.     

Complex new materials from simple chemistry: Combining an amino‐substituted polysiloxane and carboxylic acids

Changes in rheological, adhesive, and swelling properties of quaternary salts, made by adding one of eight mono‐ or six α,ω‐alkanedioic acids (the latter with two to six or nine carbon atoms) to 6‐7PSil (a polysiloxane with 6%–7% of the monomer units contain a 3‐aminopropyl group) have been correlated with the salt structures. The simple acid‐base chemistry initiates drastic changes in the bulk properties of the materials that depend on the amount and type of the added acid. Thus, the quaternized forms of the 6‐7PSil have significantly enhanced viscoelastic and adhesive properties compared to those of the initial polysiloxane, and they can swell selectively liquids based on their polarity. Also, interpenetrating networks have been made in situ by photopolymerization of salts with vinylic carboxylic acids. DFT calculations on model systems consisting of dimethylammonium α,ω‐alkanedioate salts with two to six carbon atoms provide insights into the interactions responsible for the unexpected dependence of the properties of the 6‐7PSil salts on the chain lengths of the diacids. The potential for applying the methodologies described here to systems with other amino‐substituted polymers and other acid types is noted. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3851–3861     

Synthesis and mesomorphism of ionic self-assembled complexes of anthraquinones

Anthraquinones are known to exhibit mesomorphism upon appropriate substitutions. In this report, the concept of ionic self-assembly has been applied to design and synthesise new anthraquinone-based liquid crystals. Four different anthraquinones were used as polyelectrolytes which form ionic complexes with double-tail ammonium surfactants. The chemical structures were characterised by spectral techniques and elemental analysis. The thermal behaviour of the complexes was investigated by polarising optical microscopy, differential scanning calorimetry, thermogravimetric analysis and X-ray diffraction studies. All these complexes display lamellar mesomorphism. The amphotropic nature of the complexes has also been studied.     

Betaine and Carnitine Derivatives as Herbicidal Ionic Liquids

This study focused on the synthesis and subsequent characterization of herbicidal ionic liquids based on betaine and carnitine, two derivatives of amino acids, which were used as cations. Four commonly used herbicides (2,4‐D, MCPA, MCPP and Dicamba) were used as anions in simple (single anion) and oligomeric (two anions) salts. The obtained salts were subjected to analyzes regarding physicochemical properties (density, viscosity, refractive index, thermal decomposition profiles and solubility) as well as evaluation of their herbicidal activity under greenhouse and field conditions, toxicity towards rats and biodegradability. The obtained results suggest that the synthesized herbicidal ionic liquids displayed low toxicity (classified as category 4 compounds) and showed similar or improved efficacy against weed compared to reference herbicides. The highest increase was observed during field trials for salts containing 2,4‐D as the anion, which also exhibited the highest biodegradability (>75 %).     

Alkoxide-Promoted Selective Hydroboration of N-Heteroarenes: Pivotal Roles of in situ Generated BH3 in the Dearomatization Process

While numerous organo(metallic)catalyst systems were documented for dearomative hydroboration of N-aromatics, alkoxide base catalysts have not been disclosed thus far. Described herein is the first example of alkoxide-catalyzed hydroboration of N-heteroaromatics including pyridines, providing a broad range of reduced N-heterocycles with high efficiency and selectivity. Mechanistic studies revealed an unprecedented counterintuitive dearomatization pathway, in which 1) pyridine-BH₃ adducts undergo a hydride attack by alkoxyborohydrides, 2) in situ generated BH₃ serves as a catalytic promoter, and 3) 1,4-dihydropyridyl borohydride is in a predominant resting state.     

The role of inorganic nanoparticle on ion conduction of epoxy-based solid polymer electrolytes for lithium-ion batteries

Abstract

Recently, extensive efforts have focused on the development of solid polymer electrolytes (SPEs) requiring high mechanical performance without sacrificing ion conductivity. To develop such a SPE, we incorporate robust silica mesoporous particles (SMP) into the epoxy-based SPEs, and increasing the SMP content raises the glass transition temperature of the SPEs. This enables to increase the mechanical properties of the SPEs, supported by the microstructural investigation showing a highly compact structure. Ionic conductivities of these SPEs follow Vogel temperature dependence, and increasing the silica nanoparticle content leads to a slight decrease in the conductivity, consistent with the dielectric response investigation.     

Extraction Properties of Oligodentate Carbamoylmethylphosphine Oxides and β-Aminophosphine Oxides Toward Lanthanides and Rhenium(VII)

Abstract

The extraction properties of a series of carbamoylmethylphosphine oxides and β-aminophosphine oxides with lanthanide metal ions is presented. Tris[bis(2-diphenyl- phosphorylethyl)-aminoethyl]amine is shown to be highly effective for extraction of Re(VII).     

Effects of additives and post‐treatment on the thermoelectric performance of vapor‐phase polymerized PEDOT films

Vapor‐phase polymerization (VPP) is an important method for the fabrication of high‐quality conducting polymers, especially poly(3,4‐ethylenedioxythiophene) (PEDOT). In this work, the effects of additives and post‐treatment solvents on the thermoelectric (TE) performance of VPP‐PEDOT films were systematically investigated. The use of 1‐butyl‐3‐menthylinidazolium tetrafluoroborate ([BMIm][BF₄], an ionic liquid) was shown to significantly enhance the electrical conductivity of VPP‐PEDOT films compared with other additives. The VPP‐PEDOT film post‐treated with mixed ethylene glycol (EG)/[BMIm][BF₄] solvent displayed the high power factor of 45.3 μW m^?1 K^?2 which is 122% higher than that prepared without any additive or post‐treatment solvent, along with enhanced electrical conductivity and Seebeck coefficient. This work highlighted the superior effect of the [BMIm][BF₄] additive and the EG/[BMIm][BF₄] solvent post‐treatment on the TE performance of the VPP‐PEDOT film. These results should help with developing the VPP method to fabricate high‐performance PEDOT films. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 1738–1744