1‐Amino‐1‐hydrazo‐2,2‐dinitroethene – a Hazard Warning

1‐Amino‐1‐hydrazo‐2,2‐dinitroethene ( 2 ) has been observed to spontaneously decompose with considerable violence during storage. Its preparation and handling should be regarded as potentially hazardous.     

Water‐borne melamine–formaldehyde‐cured epoxy–acrylate corrosion resistant coatings

Organic protective coatings are widely used in corrosion control. However, environmental standards establish that the volatile organic compounds either must be removed or controlled at the lowest possible levels. The carcinogenic environmental impact of volatile organic compounds has led to the substitution of solvent‐borne coatings by water‐borne coating systems. Among recently developed water‐borne coatings, epoxy‐ and acrylic‐based coatings have a special significance over other reported water‐borne systems. Keeping in mind, the importance of water‐borne coatings in the present work, we report the synthesis of water‐borne epoxy–acrylate (EpAc) and melamine–formaldehyde (MF) as well as formulation of their anticorrosive coatings. The structural elucidation of MF‐cured EpAc was carried out by FTIR, ¹H NMR, and ¹³C NMR spectroscopic techniques. The coatings of EpAc‐MF were applied on mild steel strips and were evaluated for physicochemical, physicomechanical characterization, and the anticorrosive performance under different environmental conditions. The present coating system EpAc coatings exhibited superior performance as compared to the reported water‐borne epoxy–acrylatecoatings. The presence of melamine–formaldehyde in the resin increases the scratch hardness, impact resistance, alkali resistance, and thermal stability of these coatings. EpAc‐MF‐1 was found to cure at ambient temperature and exhibit good physicomechanical properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Heat‐resistant hydrophobic–oleophobic coatings

Thermally and chemically durable hydrophobic oleophobic coatings, containing different ceramic particles such as SiO₂, SiC, Al₂O₃, which can be alternative instead of Teflon, have been developed and applied on the aluminum substrates by spin‐coating method. Polyimides, which are high‐thermal resistant heteroaromatic polymers, were synthesized, and fluor oligomers were added to these polymers to obtain hydrophobic–oleophobic properties. After coating, Al surface was subjected to Taber‐abrasion, adhesion, corrosion, and thermal tests. The effects of the particle size of ceramic powders, organic matrix, and heat on the coating material were investigated. Coating material was characterized by FTIR spectrophotometer. Surface properties and thermal resistance of the coating materials were investigated by SEM and TGA analyses. After thermal curing, contact angles of these coatings with H₂O and n‐hexadecane were measured. It was observed that coatings like ceramic particles are more resistant against scratch and abrasion than the other coatings. Also, they are harder than coatings, which do not include ceramic particles. It was seen that coatings, containing Fluorolink D10H, have high‐contact angles with water and n‐hexadecane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2386–2392, 2006     

Silver Salt of 4,6‐Diazido‐N‐nitro‐1,3,5‐triazine‐2‐amine – Characterization of this Primary Explosive

A new primary explosive, the silver salt of 4,6‐diazido‐N‐nitro‐1,3,5‐triazine‐2‐amine (AgDANT), was synthesized and characterized. AgDANT was prepared with a 97 % yield and characterized by IR spectroscopy, single‐crystal X‐ray diffraction, and DTA. The crystal density of AgDANT is 2.530 g cm⁻³ and the molecule consists of a centro‐symmetric dimer with a high degree of planarity. The intramolecular Ag Ag distance is relatively low (331 pm) and can be considered as a strong argentophilic interaction. AgDANT is non‐hygroscopic and its solubility in water (1.27 mg in 100 mL at 23 °C) is on a similar level of solubility to that of silver azide. The sensitivity of AgDANT to impact is slightly higher than that for MF, sensitivity to friction is the same as for LA, and sensitivity to electric discharge is between that for LS and MF. Initiation efficiency of AgDANT was tested in electric detonators and compared to dextrinated lead azide (initiation efficiency of AgDANT is 40 mg for PETN secondary charge). The thermal resistance of detonators with AgDANT is satisfactory; all detonators were fully functional after exposure at 65 °C (30 d) and 85 °C (2 d).     

Poly(1,3‐disila‐1,3‐diphenyl‐2‐oxaindane)– poly(dimethylsiloxane) block copolymers

The hydrolytic condensation of 1,3‐dichloro‐1,3‐disila‐1,3‐diphenyl‐2‐oxaindane under neutral conditions produced α'ω‐dihydroxy‐1,3‐disila‐1,3‐diphenyl‐2‐oxaindane (polymerization degree ≈ 4). The homofunctional condensation of α'ω‐dihydroxy‐1,3‐disila‐1,3‐diphenyl‐2‐oxaindane in a toluene solution and in the presence of activated carbon was performed, and dihydroxy‐containing oligomers with various degrees of condensation were obtained. Through the heterofunctional condensation of dihydroxy‐containing oligomers with α'ω‐dichlorodimethylsiloxanes in the presence of amines, corresponding block copolymers were obtained. Gel permeation chromatography, differential scanning calorimetry, thermomechanical analysis, thermogravimetry, and wide‐angle roentgenography investigations were carried out. Differential scanning calorimetry and roentgenography studies of the block copolymers showed that their properties were determined by the ratio of the lengths of the flexible and linear poly(dimethylsiloxane) and rigid poly(1,3‐disila‐1,3‐diphenyl‐2‐oxaindane) fragments in the macromolecular chain. At definite values of the lengths of the flexible and rigid fragments, a microheterogeneous structure was observed in the synthesized block copolymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1409–1417, 2002; DOI 10.1002/app.10335     

Preparation of polystyrene/toluene‐2,4‐ di‐isocyanate–modified montmorillonite hybrid

A novel selective interlamellar modification of cetyltrimethylammonium bromide‐exchanged montmorillonite (MMT) by toluene‐2,4‐di‐isocyanate (TDI) has been successfully obtained, and a polystyrene/TDI‐modified MMT hybrid has been prepared. After the interlamellar modification, TDI was grafted to hydroxyl groups of the MMT, and the orientation of cetyltrimethylammonium in the interlayer space changed from a bilayer lying flat structure to a double‐layer inclined one. The structures of the TDI‐modified MMT and the hybrid were characterized by Fourier transform infrared (FTIR) spectra, powder X‐ray diffraction (XRD), and transmission electron microscopy (TEM) techniques. A schematic model of the TDI‐modified MMT structure was also presented. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2201–2205, 2000     

Tetraacetyl‐dibenzyl‐hexaazaisowurtzitane Nitrosation – Studies on Scale‐up Synthesis of HNIW

A study made on 2,4,6,8‐tetraacetyl‐10,12‐dibenzyl‐2,4,6,8,10,12‐hexaazaisowurtzitane (TADBIW) nitrosation in acetic acid to 2,4,6,8‐tetraacetyl‐10,12‐dinitroso‐2,4,6,8,10,12‐hexaazaisowurtzitane (TADNOIW) allows the reaction time to be considerably shortened. During the study, the reaction yield was found to be affected by variables such as temperature, time and UV radiation. The major factor controlling the reaction rate was found to be the concentration of NO₂ molecules in the reaction mixture. Under optimal conditions the product is obtained in a 90–93% yield after 6 h of the reaction conducted at 70 °C. UV radiation increases the reaction rate, yet the product obtained is of inferior purity on account of the by‐product formed.     

Properties and pervaporation characteristics of chitosan–poly(N‐vinyl‐2‐pyrrolidone) blend membranes for MeOH–MTBE

Clear blends of chitosan with poly(N‐vinyl‐2‐pyrrolidone) (PVP) made from aqueous solutions appear to be miscible from visual appearance. Infrared (IR) spectra used to investigate the carbonyl—hydroxyl hydrogen bonding in the blends indicated compatibility of two polymers on a molecular level. The IR spectra were also used to determine the interaction change accessing with increasing temperature and indicated that a significant conformational change occurred. On the other hand, the blend membranes were evaluated for separation of methanol from methyl tert‐butyl ether. The influences of the membrane and the feed compositions were investigated. Methanol preferentially permeates through all the tested membranes, and the partial flux of methanol significantly increase with the poly(N‐vinyl‐2‐pyrrolidone) content increasing. The temperature dependence of pervaporation performance indicated that a significant conformational change occurred with increasing temperature. Combined with the IR results, the pervaporation properties are in agreement with characteristics of interaction between chain–chain within the blend membranes. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1452–1458, 1999     

Polyether–maleimide‐based crosslinked self‐healing polyurethane with Diels–Alder bonds

The Diels–Alder (DA) reaction is particularly desirable for the preparation of heat‐stimuli self‐healing polymeric materials because of its thermal reversibility, high yield, and minimal side reactions. Some attempts were conducted to synthesize polyether–maleimide‐based crosslinked self‐healing polyurethane with DA bonds (C‐PEMIPU–DA) through the reactions of the prepolymer (polymeric MDI/PBA‐1000) functionalized by furfuryl amine and polyether–maleimide without benzene in this study. The structures of intermediates and C‐PEMIPU–DA were first confirmed by ¹H‐NMR, Fourier transform infrared spectroscopy, and differential scanning calorimetry. Next, the thermal reversibility and the self‐healing performance of C‐PEMIPU–DA were studied by ¹H‐NMR, polarizing optical microscopy, tensile testing, and a sol–gel process. The results show that C‐PEMIPU–DA exhibited interesting properties of thermal reversibility and self‐healing. The polymers could be applied to self‐healing materials or recyclable materials in the fields of the repair of composite structures and aging parts because of their thermosetting properties at room temperature and thermoplasticity at higher temperatures. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41944.     

Synthesis of styrene–ethylene–butylene–styrene triblock copolymer‐g‐polylactic acid copolymer and its potential application as a toughener for polylactic acid

The copolymer of styrene–ethylene–butylene–styrene triblock copolymer‐g‐polylactic acid (SEBS‐g‐PLA) was successfully prepared using a novel solvothermal synthetic method, in which the graft copolymerization of PLA and SEBS was simply performed in cholorform solution at 100–150°C with benzoyl peroxide (BPO) as initiator. The effect of various factors including the reaction temperature and time and the content of BPO and PLA on the graft copolymerization was investigated in detail. It is found that the optimal reaction condition for the grafted copolymers SEBS‐g‐PLA was 120°C for 5 h, while the optimal formulation of SEBS/PLA/BPO was 5 g/2 g/0.5 g in 30 mL chloroform. The properties and microstructures of the obtained SEBS‐g‐PLA copolymers were also studied. The tensile strength and elongation at break were higher than that of pure SEBS and improved with the increase of grafting degree. In addition, SEBS‐g‐PLA copolymer possessed two‐phase structure with vague phase boundaries. The as‐prepared SEBS‐g‐PLA copolymers can be used as the toughening component to improve the impact strength of PLA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Highly (≥98%) Stereo‐ and Regioselective Trisubstituted Alkene Synthesis of Wide Applicability via 1‐Halo‐1‐alkyne Hydro‐ boration–Tandem Negishi–Suzuki Coupling or Organoborate Migratory Insertion

(Z)‐1‐Halo‐1‐alkenylboranes ( 7 ), preparable in 80–90% yields as ≥98% isomerically pure compounds via hydroboration of 1‐halo‐1‐alkynes, have been converted to a wide range of trisubstituted alkenes via three different routes in the tail‐to‐head ( T ‐to‐ H ) direction, i.e., (i) palladium‐catalyzed Negishi–Suzuki tandem alkenylation, (ii) treatment with organolithium or Grignard reagents to generate α‐bromo‐1‐alkenylboronate complexes that can undergo migratory insertion of a carbon group (R²) to form (E)‐alkenylboranes with inversion of alkene configuration (≥98% inversion), followed by fluoride‐promoted Suzuki alkenylation, and (iii) Negishi coupling to generate (Z)‐alkenylboranes in ≥98% retention of configuration, followed by treatment with organolithium or Grignard reagents to produce trisubstituted alkenes with reversed stereo configurations. The synthetic utility of the present methodology has been demonstrated in the highly selective synthesis of the side chain of scyphostatin in 28% yield over nine steps in the longest linear sequence from allyl alcohol. Thus, this new tandem protocol has been emerged as the most widely applicable and highly selective route to trisubstituted alkenes including those that are otherwise difficult to prepare.     

Processing–Nanostructure–Property Relationships of All‐Polyethylene Composites Reinforced by Flow‐Induced Oriented Crystallization of UHMWPE

All‐polyethylene composites exhibiting substantially improved toughness/stiffness balance are readily produced during conventional injection molding of high density polyethylene (HDPE) in the presence of bimodal polyethylene reactor blends (RB40) containing 40 wt% ultrahigh molar mass polyethylene (UHMWPE) dispersed in HDPE wax. Scanning electron microscopy (SEM) and differential scanning calorimetry (DSC) analyses shows that flow‐induced crystallization affords extended‐chain UHMWPE nanofibers forming shish which nucleates HDPE crystallization producing shish‐kebab structures as reinforcing phases. This is unparalleled by melt compounding micron‐sized UHMWPE. Injection molding of HDPE with 30 wt% RB40 at 165 °C affords thermoplastic all‐PE composites (12 wt% UHMWPE), improved Young's modulus of 3400 MPa, tensile strength of 140 MPa, and impact resistance of 22.0 kJ/m². According to fracture surface analysis, the formation of skin‐intermediate‐core structures accounts for significantly improved impact resistance. At constant RB40 content both morphology and mechanical properties strongly depend upon processing temperature. Upon increasing processing temperature from 165 °C to 250 °C the average shish‐kebab diameter increases from the nanometer to micron range, paralleled by massive loss of self‐reinforcement above 200 °C. The absence of shish‐kebab structure at 250 °C is attributed to relaxation of polymer chains and stretch‐coil transition impairing shish formation.     

Phosphorus‐containing poly(ester‐imide)–polydimethylsiloxane copolymers

New phosphorus‐containing poly(ester‐imide)‐polydimethylsiloxane copolymers were prepared by solution polycondensation of 1,4‐[2‐(6‐oxido‐6H‐dibenz < c,e > < 1, 2 > oxaphosphorin‐6‐yl)]naphthalene‐bis(trimellitate) dianhydride with a mixture of an aromatic diamine (1,3‐bis(4‐aminophenoxy)benzene) and α,ω‐bis(3‐aminopropyl)oligodimethylsiloxane of controlled molecular weight, in various ratios. Poly(amic acid) intermediates were converted quantitatively to the corresponding polyimide structures using a solution imidization procedure. The polymers are easily soluble in polar organic solvents, such as N‐methyl‐2‐pyrrolidone and N,N‐dimethylformamide, as well as in less polar solvents such as tetrahydrofuran. They show good thermal stability, the decomposition temperature being above 370 °C. The glass transition temperatures are in the range 165–216 °C. Solutions of the polymers in N‐methyl‐2‐pyrrolidone exhibit photoluminescence in the blue region. Copyright © 2010 Society of Chemical Industry     

Preparation and high‐temperature behavior of HfC–SiC nanocomposites derived from a non‐oxygen single‐source‐precursor

A single‐source precursor for the preparation of HfC‐SiC ceramics was synthesized via a Grignard reaction using bis(cyclopentadienyl)hafnium(IV) dichloride, trans‐1,4‐dibromo‐2‐butene, and (chloromethyl)trimethylsilane as raw materials. The composition, structure, pyrolysis process and high‐temperature behavior of the precursor were investigated. The results show that the precursor with a backbone comprising Hf–C, Si–C and CH=CH groups exhibits good solubility in common solvents, such as tetrahydrofuran, dimethylbenzene, and chloroform. Pyrolysis of the precursor at 1000°C yielded a microcrystalline HfC phase with a ceramic yield of 63.86 wt%. The pyrolytic products at 1600°C were HfC–SiC nanocomposite ceramics, which exhibited good thermal stability up to 2400°C. The formation of a (Hf,Si)C solid‐solution would be beneficial for densification during the sintering process. The non‐oxygen structure, high ceramic yield, homogeneous composition and excellent high‐temperature behavior of the pyrolytic products make the as‐prepared precursor a promising material for the preparation of high‐performance ultra‐high‐temperature ceramics.     

Glass‐transition temperature–conversion relationship for an epoxy–hexahydro‐4‐methylphthalic anhydride system

The DGEBA–MHHPA epoxy system has found increasing applications in microelectronics packaging, making crucial the ability to understand and model the cure kinetics mechanism accurately. The present article reports on work done to elucidate an appropriate model, modified from the empirical DiBenedetto's equation, to relate the glass‐transition temperature (T_g) to the degree of conversion for a DGEBA–MHHPA epoxy system. This model employs the ratio of segmental mobility for crosslinked and uncrosslinked polymers, λ, to fit the model curve to the data obtained. A higher ratio value was shown to indicate a more consistent rate of increase of T_g in relation to the degree of conversion, while a lower value indicated that the rate of T_g increase was disproportionately higher at higher degrees of conversion. The best fit value of λ determined by regression analysis for the DGEBA–MHHPA epoxy system was 0.64, which appeared to be higher than for those previously obtained for other epoxy systems, which ranged from 0.43–0.58. The highest T_g value obtained experimentally, T_{g max}, was 146°C, which is significantly below the derived theoretical maximum T_g∞ value of 170. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 511–516, 2000     

Dye‐affinity hollow‐fibres and their lysozyme adsorption–desorption characteristics

Dye‐affinity adsorption is increasingly used for protein separation. Hollow‐fibres have advantages as adsorbents in comparison to conventional bead supports because they are not compressible and can eliminate internal diffusion limitations. The aim of this study was to explore in detail the performance of polyamide hollow‐fibres to which Reactive Green HE‐4BD was attached for adsorption of lysozyme. The hollow‐fibre was characterized by scanning electron microscopy. These dye‐carrying hollow‐fibres (26.3 µmol g^?1) were used in the lysozyme adsorption–elution studies. The effect of initial concentration of lysozyme and medium pH on the adsorption efficiency of dye‐attached hollow‐fibres was studied in a batch system. The non‐specific adsorption of lysozyme on the polyamide hollow‐fibres was 1.8 mg g^?1. Reactive Green HE‐4BD attachment significantly increased the lysozyme adsorption up to 41.1 mg g^?1. Langmuir adsorption model was found to be applicable in interpreting lead adsorption by Reactive Green HE‐4BD attached hollow fibres. Significant amount of the adsorbed lysozyme (up to 95%) was eluted in 1 h in the elution medium containing 1.0 M NaSCN at pH 8.0. In order to determine the effects of adsorption conditions on possible conformational changes of lysozyme structure, fluorescence spectrophotometry was employed. We concluded that polyamide dye‐affinity hollow‐fibres can be applied for lysozyme adsorption without causing any significant conformational changes. Repeated adsorption–elution processes showed that these dye‐attached hollow‐fibres are suitable for lysozyme adsorption. © 2001 Society of Chemical Industry     

A preliminary evaluation of a continuous‐flow reactor for liquid–liquid–solid phase‐transfer catalyzed synthesis of n‐butyl phenyl ether

This study evaluates the feasibility of using a continuous‐flow stirred vessel reactor (CFSVR) to synthesize n‐butyl phenyl ether (ROPh) from n‐butyl bromide (RBr) and sodium phenolate (NaOPh) by liquid–liquid–solid phase‐transfer catalysis (triphase catalysis). The factors affecting the preparation of triphase catalysts, the etherification reaction in a batch reactor, and the performance in a CFSVR were investigated. The kinetic study with a batch reactor indicated that when the initial concentration of NaOPh or RBr was high, the conversion of RBr would depend on the initial concentration of both RBr and NaOPh. The reaction can be represented by a pseudo‐first‐order kinetic model when the concentration of NaOPh is in proper excess to that of RBr, and the apparent activation energy is 87.8 kJ mol^?1. When the etherification reaction was carried out in the CFSVR, the catalyst particles did not flow out of the reactor, even at a high agitation speed. The conversion of RBr in the CFSVR was, as predicted, lower than that in the batch reactor, but was higher than the theoretical value because the dispersed phase is not completely mixed. Copyright © 2004 Society of Chemical Industry     

Polypropylene–clay blends compatibilized with MAH‐g‐POE

A series of new Polypropylene (PP)–clay blends, containing 5 wt % clay, were prepared by melt compounding with maleic anhydride grafted poly(ethylene‐co‐octene) (MAH‐g‐POE) as the compatibilizer by varying its content from 0 to 20 wt %. The effect of MAH‐g‐POE on the PP–clay miscibility was examined by X‐ray diffraction (XRD), scanning electronic microscope (SEM) observation, differential scanning calorimeter (DSC) analysis, dynamic mechanical thermal analysis (DMTA), and rheological testing in sequence. The results showed that the addition of MAH‐g‐POE could improve the dispersion of clay layers in PP matrix and promoted the interaction between PP molecules and clay layers. At 10 wt % MAH‐g‐POE, the PP–clay blend exhibited a highest value of Tc,onset and Tg as well as a biggest melt storage modulus (G′), indicating the greatest PP–clay interaction. On the other hand, improved toughness and stiffness coexisted in blends with 5–10 wt % loading of MAH‐g‐POE. In view of SEM and DMTA observations, MAH‐g‐POE was well miscible with the PP matrix, even with the concentration up to 20 wt %. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 2558–2564, 2006     

Acid–base behavior of an oligomer of 3‐amino‐1,2,4‐triazole

We report the acid–base behavior of OATA, an oligomer synthesized from 3‐amino‐1,2,4‐triazole (ATA). We analyze the UV–vis spectroscopy at different media, and we analyze and discuss the acid–base equilibria taking into account tautomeric equilibria at different pH. The low aqueous solubility at neutral pH can be attributed to the neutral form. Indeed, OATA was synthesized in an ordinary filter paper, which can be used as a sensor for ammonia as well as endpoint indication. Using the OATA‐containing paper, ammonia concentrations in a solution as low as 5 ppm could be measured. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

1,2‐propanediol–cellulose–acrylamide graft copolymers

1,2‐Propanediol–cellulose–acrylamide graft copolymers (PCACs) were developed for enhanced oil recovery. They were prepared with acrylamide and 1,2‐propanediol (PDO)–cellulose, which was formed through the addition of glycols to cellulose by the Shotten–Baumann reaction between 3‐chloro‐1,2‐propanediol and cellulose. The graft copolymerization was initiated with a redox system between Ce⁴⁺ and glycols in cellulose. The infrared spectrum of PDO–cellulose had some characteristic absorption bands around 2960 (νC? H) and 1050 cm^?1 (νC? O) that also appeared for the PDO group and pyranose ring of cellulose, respectively. The rate of Ce⁴⁺ consumption by PDO–cellulose was investigated through the calculation of the overall kinetic constant from the slopes of ln(D ? D_R) versus time (where D is the absorbance and D_R is the absorbance of the original polysaccharide solution) The results showed that PDO–cellulose had high reactivity and that there were two mechanisms of oxidation by Ce⁴⁺ with PDO–cellulose. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3022–3029, 2004