N-acryloyl,N′-cyanoacetohydrazide as a thermal stabilizer for rigid poly(vinyl chloride)

N-Acryloyl,N′-cyanoacetohydrazide (ACAH) and its complexes with some metal ions have been investigated as thermal stabilizers for rigid poly(vinyl chloride) (PVC). Their stabilizing efficiencies have been measured by the continuous potentiometric determination of the evolved hydrogen chloride gas from the degradation process and by the extent of discoloration of the degraded samples compared with some conventional thermal stabilizers. The efficiency of blending ACAH with conventional thermal stabilizers has been investigated. A probable mechanism for the stabilizing action of ACAH is also proposed. © 1998 SCI.     

Functionalized polymer foams as metal ion chelating agents with rapid complexation kinetics

Foams prepared from vinylbenzyl chloride and crosslinked with divinylbenzene were functionalized with trialkylphosphite and tetralkylvinylidene diphosphonate. It was determined that the foams could be uniformly functionalized. Batch studies with the functionalized foams show that high levels of metal ion complexation can be achieved. Foams may therefore offer an important alternative to beads for rapid complexation reactions due to their highly porous structure. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1911–1916, 1998     

Synthesis,characterization, and metal complexation of poly(N‐phenylmaleimide‐co‐acrylic acid) and poly(N‐phenylmaleimide‐co‐acrylamide) as polychelatogens in aqueous solution

We carried out the free‐radical copolymerization of N‐phenylmaleimide with acrylic acid and acrylamide with an equimolar feed monomer ratio. We carried out the synthesis of the copolymers in dioxane at 70°C with benzoyl peroxide as the initiator and a total monomer concentration of 2.5M. The copolymer compositions were obtained by elemental analysis and ¹H‐NMR spectroscopy. The hydrophilic polymers were characterized by elemental analysis, Fourier transform infrared spectroscopy, ¹H‐NMR spectroscopy, and thermal analysis. Additionally, viscosimetric measurements of the copolymers were performed. Hydrophilic poly(N‐phenylmaleimide‐co‐acrylic acid) and poly(N‐phenylmaleimide‐co‐acrylamide) were used for the separation of a series of metal ions in the aqueous phase with the liquid‐phase polymer‐based retention method in the heterogeneous phase. The method is based on the retention of inorganic ions by the polymer in conjunction with membrane filtration and subsequent separation of low‐molecular‐mass species from the formed polymer/metal‐ion complex. The polymer could bind several metal ions, such as Cr(III), Co (II), Zn(II), Ni(II), Cu(II), Cd(II), and Fe(III) inorganic ions, in aqueous solution at pH values of 3, 5, and 7. The interaction of the inorganic ions with the hydrophilic polymer was determined as a function of pH and a filtration factor. Hydrophilic polymeric reagents with strong metal‐complexing properties were synthesized and used to separate those complexed from noncomplexed ions in the heterogeneous phase. The polymers exhibited a high retention capability at pH values of 5 and 7. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Synthesis,characterization, and properties of low viscosity tetra‐functional epoxy resin N,N,N′,N′‐ tetraglycidyl‐3,3′‐diethyl‐4,4′‐diaminodiphenylmethane

Tetra‐functional epoxy resin N,N,N′,N′‐tetraglycidyl‐3,3′‐diethyl‐4,4′‐diaminodiphenylmethane (TGDEDDM) was synthesized and characterized. The viscosity of TGDEDDM at 25°C was 7.2 Pa·s, much lower than that of N,N,N′,N′‐tetraglycidyl‐4,4′‐diaminodiphenylmethane (TGDDM). DSC analysis revealed that the reactivity of TGDEDDM with curing agent 4,4′‐diamino diphenylsulfone (DDS) was significantly lower than that of TGDDM. Owing to its lower viscosity and reactivity, TGDEDDM/DDS exhibited a much wider processing temperature window compared to TGDDM/DDS. Trifluoroborane ethylamine complex (BF₃‐MEA) was used to promote the curing of TGDEDDM/DDS to achieve a full cure, and the thermal and mechanical properties of the cured TGDEDDM were investigated and compared with those of the cured TGDDM. It transpired that, due to the introduction of ethyl groups, the heat resistance and flexural strength were reduced, while the modulus was enhanced. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40009.     

Drug complexation and physicochemical properties of vinylpyrrolidone‐N,N′‐dimethylacrylamide copolymers

Solid dispersions of the nonsteriodal antiinflammatory drug (NSAID) 2′,4′‐difluoro‐4‐hydroxy‐(1,1′‐biphenyl)‐3‐carboxylic acid (DIF) with the water‐soluble random copolymer poly(N‐vinyl‐2‐pyrrolidone‐co‐N,N′‐dimethylacrylamide) (VP‐co‐DMAm) were prepared by the solvent method (coevaporates) and melting DIF/VP‐co‐DMAm (cofused) physical mixtures. Differential scanning calorimetry (DSC), infrared spectroscopy (FTIR), and X‐ray diffraction (XRD) were used to elucidate the possible interaction between the NSAID drug and VP‐co‐DMAm in cofused and coevaporated polymer–drug solid dispersions. The XRD and FTIR studies suggest the presence of physical interactions with formation of a charge transfer complex between DIF and the VP‐co‐DMAm copolymers as a consequence of the coevaporation or cofusion processes. In solution, dynamic and equilibrium solubility studies were determined to elucidate the mechanism of interaction between DIF and VP‐co‐DMAm copolymers. Thermodynamics data about the DIF: VP‐co‐DMAm dissolution process indicate that the coevaporated systems are more stable that the cofused systems. The dissolution of the cofused and coevaporated systems was diffusion controlled and the dissolution kinetics followed the Noyes–Whitney and the Levich equations. Molecular simulations using semiempirical quantum chemical calculations reinforce the experimental results, suggesting that the improvement in the DIF solubility could be attributed to the charge transfer complex formation between the drug and VP‐co‐DMAm copolymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1337–1347, 2004     

Hydrodynamic properties for N,N,N′,N′‐tetraalkyl diglycolamides dissolved in n‐dodecane system

N,N,N′,N′‐tetraoctyl diglycolamide (TODGA) and N,N,N′,N′‐tetra(2‐ethylhexyl) diglycolamide (T2EHDGA) have been identified as promising extractants for actinide partitioning from high‐level nuclear waste. These extractants are proposed to be used along with suitable phase modifiers, viz. N,N‐dihexyl octanamide (DHOA), tri‐n‐butyl phosphate (TBP) and 2‐decanol dissolved in n‐dodecane. Hydrodynamic parameters, viz. density, viscosity and interfacial tension (IFT) are important for optimisation of hydrometallurgical process to ensure that there is no emulsion formation and to achieve desired phase disengagement rate. Densities and viscosities of the two extractants, viz. TODGA and T2EHDGA along with different phase modifiers have been measured over different range of compositions and temperatures (298–333 K). The viscosity data have been used to calculate the activation energy for viscous flow for each composition of solvents. The IFT values have also been measured for different solvent compositions. The viscosity and IFT data of TODGA and T2EHDGA with 2‐decanol as phase modifier appears suitable under hydrometallurgical conditions proposed for actinide partitioning. © 2011 Canadian Society for Chemical Engineering     

Synthesis,characterization, and catalytic activity of 4 mol % N,N′‐methylene bisacrylamide crosslinked poly(acrylic acid)–metal complexes

The metal‐ion complexation behavior and catalytic activity of 4 mol % N,N′‐methylene bisacrylamide crosslinked poly(acrylic acid) were investigated. The polymeric ligand was prepared by solution polymerization. The metal‐ion complexation was studied with Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) ions. The metal uptake followed the order: Cu(II) > Cr(III) > Mn(II) > Co(II) > Fe(III) > Zn(II) > Ni(II). The polymeric ligand and the metal complexes were characterized by various spectral methods. The catalytic activity of the metal complexes were investigated toward the hydrolysis of p‐nitrophenyl acetate (NPA). The Co(II) complexes exhibited high catalytic activity. The kinetics of catalysis was first order. The hydrolysis was controlled by pH, time, amount of catalyst, and temperature. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 272–279, 2004     

Study of reaction between N,N,N′,N′,N′-pentakis (hydroxymethyl) melamine and ethylene or propylene oxide

The effects of the kind and amount of oxirane (propylene or ethylene oxide), the amount of triethylamine catalyst, and the temperature on the reaction with N,N,N′,N′,N′-pentakis (hydroxymethyl) melamine (PHMM) in DMSO solution were studied. The changes in the content of reactive groups in the reaction mixture and in the final product were analyzed. The oxirane addition was shown to be accompanied by the condensation of hydroxymethyl groups in the PHMM. Optimal conditions for the synthesis and the structural formula of the s-triazine ring containing polyetherols were established. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2589–2602, 1997     

Transport of lanthanides and fission products through supported liquid membranes containing N,N,N′,N′-tetraoctyl diglycolamide (TODGA) as the carrier

Facilitated transport of trivalent lanthanides, viz. La(III), Eu(III), Lu(III) and several fission product elements such as Tc, Mo, Zr, Pd, I, Cs and Ru across a flat sheet supported liquid membrane made of PTFE impregnated with N,N,N′,N′-tetraoctyl diglycolamide (TODGA) in n-dodecane was investigated from dilute nitric acid solutions. The transport rates of lanthanides increased with nitric acid concentration in a manner similar to their distribution ratios. The trend in metal ion transport after 75 min followed the order: La > Eu > Lu > Zr > Sr > I > Pd ~ Tc > Ru > Mo ~ Cs, which was consistent even after 5 h of operation. However, the transport of I reached the maximum value of ~26% in 100 min and remained constant thereafter. In the case of Am(III) transport studies, excellent decontamination from Zr was achieved when 0.4 M oxalic acid was added to the feed solution.     

Polycondensation reaction of N,N′‐(4,4′‐oxydiphthaloyl)‐bis‐L‐methionine diacid chloride with aromatic diamines: Synthesis and properties

Several new optically active poly(amide‐imide)s have been synthesized by solution polycondensation of readily available aromatic diamines with diacid chloride containing ether‐imide and L ‐methionine moieties. Three polycondensation techniques were used: low temperature solution polycondensation, short period reflux conditions, and microwave‐assisted polycondensation. In all cases, the reactions were carried out using equimolecular amounts of the two monomers, in polar aprotic solvents. The obtained compounds were characterized by elemental analysis, solubility tests, FTIR, and ¹H NMR spectrometry. Thermal stability of the polymer was studied by thermogravimetric analysis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1038–1044, 2006     

Effect of the nature of crosslinking agent on the unusual metal ion specificity and selectivity of N,N‐bis(2‐aminoethyl)polyacrylamide

Metal ion desorbed crosslinked N,N‐bis(2‐aminoethyl)polyacrylamides showed enhanced specificity for the desorbed metal ion, and these polymers selectively rebind the desorbed metal ion from a mixture of metal ions. For this, polyacrylamide with 8 mol % divinylbenzene (DVB) and N,N′‐methylene‐bisacrylamide (NNMBA) crosslinking were prepared by solution polymerization. Diethylenetriamino functions were incorporated into the polymers by polymer analogous reactions. The complexing ability of the amino polymers were investigated toward various transition metal ions like Co(II), Ni(II), Cu(II), and Zn(II). Polymeric ligand and metal complexes were characterized by various spectral methods. The removal of the metal ion from the polymer matrix resulted in a memory for the desorbed metal ion. On rebinding, these polymers specifically rebind the desorbed metal ion and from a mixture of metal ions, it showed selectivity to the desorbed metal ion. Thus, the Cu(II) desorbed polymer specifically and selectively rebind Cu(II) ion from a mixture of Cu(II) and other metal ion. This selectivity is higher in the rigid DVB‐crosslinked system, resulting from the high rigidity of the crosslinked matrix compared to the semirigid NNMBA‐crosslinked system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Reactions taking place in the system N,N,N′,N′,N″‐ pentakis(hydroxymethyl)melamine–oxirane in aqueous media

The results of studies on effects of the amount and type of oxirane, amount of catalyst and water, and temperature on the course of reactions taking place in the system N,N,N′,N′,N″‐pentakis(hydroxymethyl)melamine (PHMM)–oxirane carried out in aqueous media are reported. Quantitative determination of the content of functional groups present in the system and of side products formed in reactions of oxirane with water, made it possible to analyze in detail the processes taking place in the system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 824–836, 2000     

A conducting nanocomposite of acetylene black with preformed poly‐N‐vinylcarbazole crosslinked by anhydrous FeCl3

A conducting nanocomposite of crosslinked poly‐N‐vinylcarbazole (CLPNVC) with nanodimensional acetylene black (AB) was prepared by oxidative crosslinking of preformed PNVC through pendant carbazole moieties in presence of anhydrous FeCl₃ as an oxidant and AB suspension in CHCl₃ medium at 65°C. The incorporation of CLPNVC moieties in the CLPNVC‐AB composite was endorsed by Fourier transform infrared analysis. Scanning electron microscopic analysis showed formation of lumpy aggregates with average sizes in the 130–330 nm ranges. The thermal stability of the CLPNVC‐AB composite was appreciably higher than that of the PNVC‐AB composite. The direct current conductivities of the composites were significantly enhanced relative to that of the PNVC homopolymer (10^?12–10^?16 S/cm) and varied in the range of 10^?4–10^?2 S/cm depending on the amount of AB loading in the CLPNVC‐AB composite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 819–824, 2006     

Succinoylation of wheat straw hemicelluloses in N,N‐dimethylformamide/lithium chloride systems

The chemical modification of native wheat straw hemicelluloses with succinic anhydride using N,N‐dimethylformamide/lithium chloride system as solvent and pyridine and/or 4‐dimethyaminopyridine as catalyst has been examined. In particular, the progress of the succinoylation reaction is studied as a function of the molar ratio of succinic anhydride/anhydroxylose unit in native hemicelluloses from 1:1 to 5:1, DMAP concentration 0.025–0.20 g, reaction temperature 40–140 °C, and reaction time 2–12 h with succinic anhydride. The degree of substitution of succinylated hemicelluloses ranges between 0.4 and 1.5 depending on the experimental conditions. FTIR and ¹H NMR spectroscopic characterization of the esterified polymers indicates a monoester substitution. The thermal stability of the esterified polymer decreases slightly upon chemical modification, but no significant further decrease in thermal stability is observed for DS ≥ 0.7. © 2001 Society of Chemical Industry     

Synthesis,characterization, and thermal properties of alternate copolymers containing N,N′‐bis(diphenylsilyl)tetraphenylcyclodisilazane

Hexamethyldisilazane was used as the starting material to synthesize N,N′‐bis(hydroxydiphenylsilanyl)tetraphenylcyclodisilazane (BHPTPC). By condensation polymerization of BHPTPC with α,ω‐bis(dialkylamino)dimethylsiloxane, a series of alternate copolymers containing N,N′‐bis(diphenylsilyl)tetraphenylcyclodisilazane was synthesized. GPC studies show that the highest molecular weight was obtained at a ratio of 1.005 : 1 (BHPTPC: α,ω‐bis(dimethyl amino)dimethylsiloxane). Data of DSC indicate that the temperature of glass transition (T_g) and temperature of melting point (T_m) decreased with the increasing of dimethylsiloxane segments units. Three stages of degradation were found in the thermogravimetric analysis curves. The activation energy of the copolymer (with m = 2, 3, and 7) was calculated by using Flynn–Wall–Ozawa method. The activation energy of the copolymer with m = 2, 3, and 7 at second stage is 214, 211, and 184 kJ/mol, respectively. Isothermal gravimetric analysis shows that for the same temperature and the same time, the weight loss of the alternate copolymer was greatly less than that of common polydimethylsiloxane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 611–617, 2007     

Synthesis,characterization, and applications of novel additives of polysiloxane containing N,N′‐bis(diphenylsilyl)tetraphenylcyclodisilazane

Three N,N′‐bis(diphenylsilyl)tetraphenylcyclodisilazane‐based derivatives, N,N′‐bis(3,3,3‐trimethyl‐1,1‐diphenyl‐disiloxanyl)tetraphenylcyclodisilazane, N‐(3,3‐dimethyl‐1,1‐diphenyl‐3‐vinyl‐disiloxanyl)‐N′‐(3,3,3‐trimethyl‐1,1‐diphenyl‐disiloxanyl)‐tetraphenylcyclodisilazane, and N,N′‐bis‐(3,3‐dimethyl‐1,1‐diphenyl‐3‐vinyl‐disiloxanyl) tetraphenylcyclodisilazane, were synthesized. These compounds were synthesized in an easy and effective route. X‐ray single‐crystal diffraction analyses showed that the four‐member rings were planar rings, and the structures are different with the different substitution. The compound N,N′‐bis‐(3,3‐dimethyl‐1,1‐diphenyl‐3‐vinyl‐disiloxanyl) tetraphenylcyclodisilazane was added to the silicone rubber as additive to enhance the thermal stability greatly increased the thermal stability of the silicone rubber, without altering the glass transition temperature. The weight loss at 350°C in nitrogen atmosphere for 24 h reduced from 55.8% for 0 wt % to 9.8% for 10 wt % addition N,N′‐Bis‐(3,3‐dimethyl‐1,1‐diphenyl‐3‐vinyl‐disiloxanyl)tetraphenylcyclodisilazane. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis,Structure, and Properties of N,N′‐Dinitrourea

Information on synthesis methods and properties of N,N′‐dinitrourea and its salts, which were reported virtually simultaneously by different authors in different publications, is summarized and systematized. Merits and drawbacks of various approaches for the synthesis of the target products are discussed. The reactivity of N,N′‐dinitrourea and its salts in the reactions of nucleophilic substitution and condensation is discussed.     

Polymer-metal complexes,based on poly(itaconic acid ester) derivatives,as catalysts for the decomposition of hydrogen peroxide

Poly(methyl itaconates) and poly(heptyl itaconates), modified with ethylene diamine (EN) and tetraethylene pentamine (TETRAEN) side chains, were complexed with cobalt and copper ions, and their efficiencies as catalysts for the decomposition of hydrogen peroxide were assessed. All the polymer complexes studied were found to be active catalysts, but it was observed that the polymers with TETRAEN side chain, when complexed with CoCl₂ and CuCl₂ were less efficient than polymers with EN side chains which were complexed with trans-dichlorobis(ethylenediamine) cobalt(III) chloride, trans-[Co(EN)₂Cl₂]Cl. One feature of interest was that when the alkyl side chain of the poly itaconate was heptyl the rate of decomposition of hydrogen peroxide was faster than when the alkyl group was methyl.