Synthesis, crystal structures and magnetic behavior of two 3D coordination polymers using N-(4/3-arboxyphenyl)iminodiacetic acids as bridging ligands

Research on structure and magnetic properties of polynuclear metal complexes to understand the structural and chemical factors governing the electronic exchange coupling mediated by multi-atom bridging ligands is of growing interest. Hydrothermal treatment of Ni(NO3)(2)center dot 6H(2)O with N-(4-carboxyphenyl)iminodiacetic acid N-4(H(3)CPIDA)] at 150 degrees C yielded a 3D coordination polymer of general formula Ni-3{N-4( CPIDA)}(2)(H2O)(3)]center dot 6H(2)O (1). An analogous network of general formula Co-3{N-3(CPIDA)}(2)(H2O)(3)]center dot 3H(2)O (2) was synthesized using N-(3-carboxyphenyl) iminodiacetic acid N-3(H(3)CPIDA)] in combination with Co(NO3)(2)center dot 6H(2)O under identical reaction condition. Both the complexes contain trinuclear secondary building unit, and crystallized in monoclinic system with space groups C2/c (1) and P2(1)/c (2), respectively. Variable temperature magnetic characterization of these complexes in the temperature range of 2-300 K indicated the presence of overall ferromagnetic and antiferromagnetic behavior for 1 and 2, respectively. Density functional theory calculations (B3LYP functional) were performed for further insight on the trinuclear units to provide a qualitative theoretical interpretation on the overall magnetic behavior of the complexes 1 and 2. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis of epoxy-terminated polymers by radical polymerization using alpha-(t-butylperoxymethyl)styrene as chain transfer agent

Epoxy-terminated polystyrene has been synthesized by radical polymerization using alpha-(t-butylperoxymethyl) styrene (TPMS) as the chain transfer agent. The chain transfer constants were found to be 0.66 and 0.80 at 60 and 70 degrees C, respectively. The presence of epoxy end groups was confirmed by functional group modification of epoxide to aldehyde by treatment with BF3.Et(2)O. Thermal stability of TPMS was followed by differential scanning calorimetry and iodimetry. Thermal decomposition of TPMS in toluene follows first order kinetics with an activation energy of 23 kcal/mol. (C) 1996 John Wiley & Sons, Inc.

Stabilization of thermal degradation of poly(methyl methacrylate) by polysulfide polymers

The thermal degradation of poly(methyl methacrylate) (PMMA) in the presence of polysulfide polymers, namely, poly( styrene disulfide) (PSD) and poly(styrene tetrasulfide) (PST) was studied using thermogravimetry (TG) and direct pyrolysis-mass spectrometric (DP-MS) analysis. Both PSD and PST were found to stabilizethe PMMA degradation, which was explained by both radical recombination and a chain-transfer mechanism. (C) 1997 John Wiley & Sons, Inc.

Reversible Swelling/Deswelling Characteristics of Ethylene Glycol Dimethacrylate Cross-Linked Poly(acrylic acid-co-sodium acrylate-co-acrylamide) Superabsorbents

Poly(acrylic acid-co-sodium acrylate-co-acrylamide) superabsorbent polymers (SAPs) cross-linked with ethylene glycol dimethacrylate (EGDMA) were synthesized by inverse suspension polymerization. The SAPs were swollen in DI water, and it was found that the equilibrium swelling capacities varied with the acrylamide content. The SAPs were subjected to reversible swelling/deswelling cycles in DI water and aqueous NaCl solution, respectively. The effect of the addition of an electrolyte on the swelling of the SAP was explored. The equilibrium swelling capacity of the SAPs was found to decrease with increasing concentration of added electrolyte in the swelling medium. The effect of the particle size of the dry SAPs on the swelling properties was also investigated. A first order model was used to describe the kinetics of swelling/deswelling, and the equilibrium swelling capacity, limiting swelling capacity, and swelling/deswelling rate coefficients were determined.

Adsorption of cationic dyes on poly(acrylic acid-co-sodium acrylate-co-acrylamide) superabsorbents

Inverse suspension polymerization was carried out to synthesize poly(acrylic acid-co-sodium acrylate-co-acrylamide) superabsorbent polymers (SAPs) crosslinked with ethylene glycol dimethacrylate (EGDMA). The equilibrium swelling capacities of the SAPs, determined by swelling them in DI water, were found to vary with the acrylamide (AM) content. The SAPs were used to adsorb four cationic dyes (Acriflavine, Auramine-O, Azure-I and Pyronin-Y). The effect of AM content in the SAPs on the adsorption of the cationic dyes was investigated. Different initial concentrations of Azure-I were used with the same amount of the SAP to explore the effect of initial dye concentration on the adsorption. The effect of the adsorbent amount was investigated by taking different amounts of SAP with a fixed initial concentration of Acriflavine. The kinetics of the dye adsorption was modeled by a first order model and the equilibrium amount of the dye adsorbed, adsorption rate coefficients, removal efficiency and partition coefficients were determined. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Photo, thermal, and ultrasonic degradation of EGDMA-crosslinked poly(acrylic acid-co-sodium acrylate-co-acrylamide) superabsorbents

Superabsorbent polymers (SAPs) based on acrylic acid (AA), sodium acrylate (SA), and acrylamide (AM) were synthesized by inverse suspension polymerization using ethylene glycol dimethacrylate as the crosslinking agent. The equilibrium swelling capacities and the rates of swelling of SAPs varied with the AM content and followed first-order kinetics. The photodegradation of SAPs in their equilibrium swollen state was carried out by monitoring their swelling capacity and the residual weight fraction. The SAPs degraded in two stages, wherein the swelling capacity increased to a maximum and then subsequently decreased. Thermogravimetric analysis of the SAPs indicated that the copolymeric superabsorbents had intermediate thermal stability between the homopolymeric superabsorbents. The activation energies of SAPs with 0, 20, and 100 mol % AM content were determined by Kissinger method and were found to be 299, 248, and 147 kJ mol-1, respectively. The ultrasonic degradation of the superabsorbents was carried out in their equilibrium swollen state, and the change in the viscosity with ultrasonication time was used to quantify the degradation. The ultrasonic degradation of AA/SA superabsorbent was also investigated at various ultrasound intensities. The degradation rate coefficients were found to increase with the intensity of ultrasound. The ultrasonic degradation of AA/SA/AM (20% AM) was also carried out, and degradation rate was found to be more than that of the AA/SA superabsorbent. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Thermal degradation kinetics of thermoresponsive poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) copolymers prepared via RAFT polymerization

Reversible addition-fragmentation chain transfer polymerization at 70 A degrees C in N,N-dimethylformamide was used to prepare poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) copolymers in various compositions to afford well-defined polymers with pre-determined molecular weight, narrow molecular weight distribution, and precise chain end structure. The copolymer compositions were determined by H-1 NMR spectroscopy. The reactivity ratios of N-isopropylacrylamide (NIPAM) and N,N-dimethylacrylamide (DMA) were calculated as r (NIPAM) = 0.838 and r (DMA) = 1.105, respectively, by the extended Kelen-Tudos method at high conversions. The lower critical solution temperature of PNIPAM can be altered by changing the DMA content in the copolymer chain. Differential scanning calorimetry and thermogravimetric analysis at different heating rates were carried out on these copolymers to understand the nature of thermal degradation and to determine its kinetics. Different kinetic models were applied to estimate various parameters like the activation energy, the order, and the frequency factor. These studies are important to understand the solid state polymer degradation of N-alkyl substituted polymers, which show great potential in the preparation of miscible polymer blends due to their ability to interact through hydrogen bonding.

Solvent-templated supramolecular isomerism in 2D coordination polymer constructed by (Ni2CoII)-Co-II nodes and dicyanamido spacers: drastic change in magnetic behaviours

Two heterometallic coordination polymers (CPs) have been prepared using (NiL)-L-II](2)Co-II (where H2L = N,N'-bis(salicylidene)-1,3-propanediamine) as nodes and dicyanamido spacers by varying the solvent for synthesis. Structural characterizations revealed that methanol assisted the formation of a two-dimensional (4,4) connected rhombic grid network of (NiL)(2)Co(NCNCN)2](infinity) (1a) whereas relatively less polar acetonitrile afforded a different superstructure {(NiL)(2)Co(NCNCN)(2)]center dot CH3CN}(infinity) (1b) with a two-dimensional (4,4) connected square grid network. The presence of acetonitrile molecules in the structure of 1b seems to change the spatial orientation of the terminal metalloligands NiL] from pseudo-eclipsed in 1a to staggered-like in 1b around the central Co(II). These structural changes in the nodes together with the conformationally flexible dicyanamido spacers, which are cis coordinated to the Co(II) in both trinuclear units, led to the differences in the final 2D network. Variable-temperature magnetic susceptibility measurements revealed that this supramolecular isomerism led to a drastic transition from spin-frustrated antiferromagnetism for 1a to a dominant ferromagnetic behaviour for 1b. The geometrical differences in Ni2Co coordination clusters (CCs) which are scalene triangular in 1a but nearly linear in 1b, are held responsible for the changes of the magnetic properties. The DFT calculations of exchange interactions between metal centres provide a clear evidence of the role played by the fundamental geometrical factors on the nature and magnitude of the magnetic coupling in these pseudo-polymorphic CPs.

Thermal and Sonochemical Degradation Kinetics of Poly(n-butyl methacrylate-co-alkyl acrylates): Variation of Chain Strength and Stability with Copolymer Composition

The thermal degradation of poly(n-butyl methacrylate-co-alkyl acrylate) was compared with ultrasonic degradation. For this purpose, different compositions of poly (n-butyl methacrylate-co-methyl acrylate) (PBMAMA) and a particular composition of poly(n-butyl methacrylate-co-ethyl acrylate) (PBMAEA) and poly(n-butyl methacrylate-co-butyl acrylate) (PBMABA) were synthesized and characterized. The thermal degradation of polymers shows that the poly(alkyl acrylates) degrade in a single stage by random chain scission and poly(n-butyl methacrylate) degrades in two stages. The number of stages of thermal degradation of copolymers was same as the majority component of the copolymer. The activation energy corresponding to random chain scission increased and then decreased with an increase of n-butyl methacrylate fraction in copolymer. The effect of methyl acrylate content, alkyl acrylate substituent, and solvents on the ultrasonic degradation of these copolymers was investigated. A continuous distribution kinetics model was used to determine the degradation rate coefficients. The degradation rate coefficient of PBMAMA varied nonlinearly with n-butyl methacrylate content. The degradation of poly (n-butyl methacrylate-co-alkyl acrylate) followed the order: PBMAMA < PBMAEA < PBMABA. The variation in the degradation rate constant with composition of the copolymer was discussed in relation to the competing effects of the stretching of the polymer in solution and the electron displacement in the main chain. (C) 2012 Society of Plastics Engineers

Nanorod to quantum dot conversion in ZnO dispersions with co-surfactants

A chemically-induced nanorod to quantum dot transition is reported in ZnO. This transition is achieved using co-surfactants in a marginally polar solvent in chimie douce (soft chemical) conditions. This is different from the physical instability driven transitions reported so far in metal nanowires and polymers. We propose a suitable mechanism for the observed phenomenon.

Synthesis and potency of long end-associative polymers for mist control

Long linear polymers that are end-functionalized with associative groups were studied as additives to hydrocarbon fluids to mitigate the fire hazard associated with the presence of mist in a crash scenario. These polymers were molecularly designed to overcome both the shear-degradation of long polymer chains in turbulent flows, and the chain collapse induced by the random placement of associative groups along polymer backbones. Architectures of associative groups on the polymer chain ends that were tested included clusters of self-associative carboxyl groups and pairs of hetero-complementary associative units.

Linear polymers with clusters of discrete numbers of carboxyl groups on their chain ends were investigated first: an innovative synthetic strategy was devised to achieve unprecedented backbone lengths and precise control of the number of carboxyl groups on chain ends (N). We found that a very narrow range of N allows the co-existence of sufficient end-association strength and polymer solubility in apolar media. Subsequent steady-flow rheological study on solution behavior of such soluble polymers in apolar media revealed that the end-association of very long chains in apolar media leads to the formation of flower-like micelles interconnected by bridging chains, which trap significant fraction of polymer chains into looped structures with low contribution to mist-control. The efficacy of very long 1,4-polybutadiene chains end-functionalized with clusters of four carboxyl groups as mist-control additives for jet fuel was further tested. In addition to being shear-resistant, the polymer was found capable of providing fire-protection to jet fuel at concentrations as low as 0.3wt%. We also found that this polymer has excellent solubility in jet fuel over a wide range of temperature (-30 to +70°C) and negligible interference with dewatering of jet fuel. It does not cause an adverse increase in viscosity at concentrations where mist-control efficacy exists.

Four pairs of hetero-complementary associative end-groups of varying strengths were subsequently investigated, in the hopes of achieving supramolecular aggregates with both mist-control ability and better utilization of polymer building blocks. Rheological study of solutions of the corresponding complementary associative polymer pairs in apolar media revealed the strength of complementary end-association required to achieve supramolecular aggregates capable of modulating rheological properties of the solution.

Both self-associating and complementary associating polymers have therefore been found to resist shear degradation. The successful strategy of building soluble, end-associative polymers with either self-associative or complementary associative groups will guide the next generation of mist-control technology.

Heterogeneous catalytic activity on Mn, Fe and Co-based metalloporphyrinic Solid Coordination Frameworks (SCFs)

Comunicación al congreso 1st European Conference on Metal Organic Frameworks and Porous Polymers, celebrado en Postdam del 11 al 14 de octubre de 2015

Phase Behavior and self-assembly of poly[N-vinylformamide-co-(acrylic acid)] copolymers under highly acidic conditions

Copolymers of N-vinylformamide and acrylic acid were synthesized by conventional aqueous free-radical polymerization. The phase behavior of the copolymer solutions was investigated through the addition of hydrochloric acid and the variation of the temperature. With a moderate content of N-vinylformamide, the copolymers showed complex phase behaviors. Under low-acidity conditions, a suspending liquid was formed, whereas under high-acidity conditions, the random copolymers could assemble into round nanoparticles with a broad particle size distribution.

Sulfonated poly(arylene-co-imide)s as water stable proton exchange membrane materials for fuel cells

A novel sulfonated poly(arylene-co-imide)s were synthesized by Ni(0) catalytic copolymerization of sodium 3-(2,5-dichlorobenzoyl)benzenesulfonate and naphthalimide dichloride monomer. The synthesized copolymers with the - SO3H group on the side-chain of polymers possessed high molecular weights revealed by their high viscosity and the formation of tough and flexible membranes. Because of the introduction of electron donating phenoxy groups into naphthalimide moieties, the hydrolysis of the imide rings was depressed. The resulting copolymers exhibited excellent water stability. The copolymer membranes display no apparently change in appearance, flexibility, and toughness after a soaking treatment in pressurized water at 140 degrees C for 250 h.

Synthesis and Characterization of One-Dimensional and Molecular M(tren)InAsS4 (M = Mn, Co, and Zn) Compounds with a Noncondensed AsS33- Unit

Four transition-metal-amine complexes incorporating indium thioarsenates with the general formula M(tren)InAsS4 (M=Mn, Co, and Zn) and a noncondensed AsS33- unit have been prepared and characterized. Single-crystal X-ray diffraction analyses show that compound 1 (M=Mn) crystallizes in the triclinic crystal system (space group: P (1) over bar) and consists of a one-dimensional (1D) inorganic (1)(infinity){[InAsS4](2-)} chain and [Mn(tren)](2+) groups bonded to the opposite sides of an eight-membered In2As2S4 ring along the backbone of the infinite inorganic chains. Compounds 2 (M=Mn), 3 (M=Zn), and 4 (M=Co) are isomorphous molecular compounds. They all crystallize in the monoclinic crystal system (space group: P2(1)/c). The Mn2+ cation of [Mn(tren)](2+) in 1 has a distorted octahedral environment, while the transition-metal cations of [M(tren)](2+) in the other three compounds locate in trigonal-bipyramidal environments.