Radiation-induced grafting of N,N-dimethylacrylamide onto polytetrafluoroethylene

Grafting of N,N-dimethylacrylamide (DMAA) onto polytetrafluoroethylene (PTFE) has been carried out by using gamma rays from a ⁶⁰Co source. Degree of grafting was affected by grafting conditions. Especially, solvent for the grafting was found to be a very significant parameter to obtain a higher grafting yield. When ethylacetate or acetone was used as the solvent, grafting yield greater than 5% was obtainable while the graftcopolymerization scarcely occurred in the presence of other kinds of solvent such as ethanol or water. Apparent activation energy of the grafting in ethylacetate was calculated to be 7.90 Kcal/mol, and initial grafting rate of it was proportional to 0.55 power of dose rate.     

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     

Grafting of N,N′-methylenebisacrylamide onto silk fibers using the vanadylacetylacetonate complex in aqueous medium

The grafting of N,N′-methylenebisacrylamide (N,N′-MBA) onto mulberry silk fibers is reported using vanadylacetylacetonate (VO(acac)₂) complex under inert atmosphere at 50°C. The effect of various variables like, concentration of N,N′-MBA and VO(acac)_2, acidity of the medium and the surfactants on the percentage grafting have been investigated. The higher rate of radical formation has been explained due to the coordination of π-electrons of the N,N′-MBA with the metal chelate which has assisted in the cleavage of M? O bond to generate radical easily. A plausible mechanism for graft copolymerization involving cyclization of N,N′-MBA prior to the grafting has been proposed.     

Radiation-induced grafting of functional acrylic monomers onto polyethylene and polypropylene films using acryloyl chloride

Summary Radiation-induced graft polymerization of acryloyl chloride onto films of polyolefins (polyethylene and polypropylene) using gamma radiation was investigated in order to establish a convenient method to obtain polymer films grafted with polyacrylic esters. Grafting was carried out by three different methods; (i) direct irradiation of film in monomer solution (ii) vapor phase irradiation method, and (iii) pre-irradiation in air. The effects of monomer concentration, radiation dose and methods of grafting, on the formation of grafted polyolefins are reported in this paper. Received: 5 April 2000/Revised version: 17 November 2000/Accepted: 20 November 2000     

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     

Thermodynamic aspects of the bovine serum albumin adsorption onto N,N′‐ diethylaminoethyl dextran microbeads

Adsorption of proteins on solid surfaces is widely studied because of its importance in various biotechnological, medical, and technical applications, e.g., biosensor cardiovascular implants and chromatography. Adsorption thermodynamics has been studied on the microbeads of N,N′‐diethylaminoethyl (DEAE) dextran anion exchanger for bovine serum albumin at 25, 30, 35 40, and 45°C. As a result some thermodynamic parameters like Freundlich constants, thermodynamic equilibrium constant (K_D), standard free energy changes (ΔG_assoc), standard entropy changes (ΔS_assoc), and standard enthalpy change (ΔH_assoc) have been evaluated. Using the linear Van't Hoff plot, the ΔH_assoc value of the system for the interaction of BSA adsorbed crosslinked DEAE dextran microbeads was determined as 12.5 kJ/mol. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Radiation-induced grafting onto wool. A kinetic analysis

The radiation-induced graft copolymerization of styrene onto wool in aqueous methanol was studied over a temperature range of 0°C to 45°C and a radiation dose-rate range of 0.05 to 2.0 Mrad/hr. The rate of grafting was found to obey the classical polymerization equation. Chain transfer to wool was found to play an important role in the grafting process, and the molecular weight of the resulting graft copolymer was found to be independent of the irradiation dose. The activation energy of the graft process changed from a value of 4.7 kcal/mole below 19°C to a value of 18.7 kcal/mole above this temperature. This phenomenon is ascribed to the formation of hydrogen-bonded systems between the protic solvent molecules and the protein chain in the wool.     

Substituierte N,N′-Bis(thiazol-2-yl)-diaminoalkane aus α-Thiocyanato-acetophenonen und N,N′-Dialkyl-diamino-alkanen

Substituted N,N′-Bis(thiazol-2-yl)-diaminoalkanes from α-Thiocyanato-acetophenones and N,N′-Dialkyl-diaminoalkanes α-Thiocyanato-acetophenones 1 react with N,N′-dialkyl-diaminoalkanes 2 in the presence of an appropriate weak acid (acetic acid, propionic acid, benzoic acid) to give the hitherto unknown N,N′-dialkyl-N,N′-bis(4-aryl-thiazol-2-yl)-diaminoalkanes 3 . As reaction medium aliphatic alcohols (ethanol, methanol), halogenated hydrocarbons (methylene chloride, chloroform, carbon tetrachloride) or dipolar-aprotic solvents (acetonitrile, dimethylformamide) can be used. - I.r., u.v., n.m.r. and mass spectroscopic data of the novel bisthiazoles 3 are reported.     

Epoxy resins based on aromatic glycidylamines. VI. Toughening of N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenylmethane by reactive additives

Mechanical properties of N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenylmethane and its mixtures with liquid bisphenol A-type epoxy resins, bisphenol A and ε-caprolactone have been studied. 4,4′-Diaminodiphenylsulfone was used as hardener. Materials with improved fracture toughness and good mechanical strength in the temperature range 20–200°C have been formulated.     

α-Substituierte Phosphonate. XXXI. Zur Reaktion von N,N,N′,N′-Tetramethylchlorformamidiniumchlorid mit P-III-Verbindungen

α-Substituted Phosphonates. XXXI. The Reaction of N,N,N′,N′-Tetramethyl Chloroformamidinium Chloride with P(III) Compounds N,N,N′,N′-Tetramethyl chloroformamidiniumchloride ( 4 ) does not react with triethyl phosphite (TEP) or isopropyl diphenylphosphinate to give the expected bisphosphoryl derivatives 7 and 11 , respectively, but primarily the monophosphorylated amidinium salts 6 and 10 respectively. The phosphine oxide 10 is stable, while 6 undergoes an elimination of ethyl chloride to the betain 8 . Even under more drastic conditions the reaction of 4 or 8 with TEP does not lead to the expected bis(dimethylamino)bisphosphonate 7 , but to the monoaminated bisphosphonate 1 , involving a reduction step. Similar reduction has been observed under mild conditions in Michaelis-Arbusov reaction of dichloromethylenimonium chloride, yielding the expected trisphosphonate 2 and the bisphosphonate 1 as a by-product.     

Syntheses and Analyses of N,N′‐Dinitrourea

N,N′‐Dinitrourea was prepared through nitration of urea at low temperature in mixed acids in 67 % yield. The prepared material was pure and found to be stable at room temperature. The properties of N,N′‐dinitrourea were analysed by: TG, DSC, ignition test in Wood's metal bath, NMR, MS, FT‐IR, gaspycnometry and BAM impact and friction sensitivity tests. N,N′‐Dinitrourea was found to have a very high density and positive oxygene balance. It was, however, found to be sensitive both to impact and friction.     

A thermodynamic study of the binding of human serum albumin onto N,N′‐diethylaminoethyl dextran microbeads

Adsorption of proteins on solid surfaces is widely studied because of its importance in various biotechnological, medical, and technical applications, e.g., biosensors, cardiovascular implants, and chromatography. Adsorption thermodynamics has been studied on the microbeads of N,N′‐diethylaminoethyl (DEAE) Dextran anion exchanger for the human serum albumin (HSA) at 25, 30, 35, 40, and 45°C. As a result, some thermodynamic parameters like Freundlich constants, thermodynamic equilibrium constant (K_D), standard free energy changes (ΔG_assoc), standard entropy changes (ΔS_assoc), and standard enthalpy change (ΔH_assoc) have been evaluated. Using the linear Van't Hoff plot, ΔH_assoc value of the system for the interaction of bovine serum albumin (BSA)‐adsorbed crosslinked DEAE dextran microbeads was determined as 20.650 kJ/mol. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3942–3947, 2006     

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     

Grafting of acrylonitrile onto allylated caesarweed fibers by potassium permanganate – N,N′‐dimethylacetamide redox pair

Caesarweed fiber, Urena lobata, was modified by successive treatment with sodium hydroxide and allylchloride in diethylether to yield an average degree of substitution of 2.73 allyl moieties per anhydroglucose unit. The presence of allyl moieties on the fiber was confirmed by infrared spectroscopy. Graft copolymerization of acrylonitrile onto the unmodified and allyl‐modified fibers was initiated by potassium permanganate –N,N′‐dimethylacetamide redox pair in aqueous medium. The allyl fiber was markedly less reactive than the unmodified fiber with graft yields for the latter a factor of 2.3 higher than those of the former. This was attributed to resonance stabilization of allylic macroradicals of the fiber. The graft yield showed positive dependence on N,N′‐dimethylacetamide concentration in the range, 9.0–45.0 × 10^?4M with P_g/P_go of up to 1.39 at the highest concentration. The conversion in graft yield was however characterized by a plateau at the latter concentration and was ascribed to termination of grafted polymer chains by methylacetylaminomethyl radical initiating species. Spectroscopic evidence in support of the latter was the absorption peak at 1680 cm^?1 for the graft copolymers, characteristic of C?O stretching vibration for tertiary amide. Acetic acid, at concentrations in the range 0.28–2.22M, was inimical to grafting of acrylonitrile onto allylfibre with P_g/P_go, of less than one. Grafting onto allylfiber showed positive temperature dependence in the range, 30–50°C with calculated activation energy of 12.3 kcal mol^?1 for the graft polymerization reaction. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Homogeneous grafting reaction of vinyl pyrrolidone onto chitosan

Modification of chitosan by grafting of vinyl pyrrolidone (VP) was carried out in homogeneous phase using potassium persulfate as redox initiator. The effect of the reaction variables on the extent of grafting was studied systematically. Values for grafting percentages up to 290% were reached. It was observed that the solubility of chitosan was markedly reduced after grafting with vinyl pyrrolidone. The grafted product is insoluble in common organic solvents as well in dilute organic and inorganic acids. However, the solubility of the grafted chitosan after adsorption of copper ions changed substantially, becoming completely soluble in dilute hydrochloric acid. This was attributed to the effect of complex formation produced by coordination of amino groups of chitosan with copper ions. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1321–1326, 1997     

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.     

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.