Chemical toughening of epoxies. II. Mechanical, thermal, and microscopic studies of epoxies toughened with hydroxyl-terminated poly(butadiene-co-acrylonitrile)

Diglycidyl ether–bisphenol-A-based epoxies toughened with various levels (0–12%) of chemically reacted liquid rubber, hydroxyl-terminated poly(butadiene-co-acrylonitrile) (HTBN) were studied for some of the mechanical and thermal properties. Although the ultimate tensile strength showed a continuous decrease with increasing rubber content, the toughness as measured by the area under the stress-vs.-strain curve and flexural strength reach a maximum around an optimum rubber concentration of 3% before decreasing. Tensile modulus was found to increase for concentrations below 6%. The glass transition temperature Tg as measured by DTA showed no variation for the toughened formulations. The TGA showed no variations in the pattern of decomposition. The weight losses for the toughened epoxies at elevated temperatures compare well with that of the neat epoxy. Scanning electron microscopy revealed the presence of a dual phase morphology with the spherical rubber particles precipitating out in the cured resin with diameter varying between 0.33 and 6.3 μm. In contrast, a physically blended rubber–epoxy showed much less effect towards toughening with the precipitated rubber particles of much bigger diameter (0.6–21.3 μm).

Chemical toughening of epoxies. I. Structural modification of epoxy resins by reaction with hydroxy-terminated poly(butadiene-co-acrylonitrile)

In an attempt to toughen the epoxy resin matrix for fiber-reinforced composite applications, a chemical modification procedure of a commercially available bisphenol-A-based epoxy resin using reactive liquid rubber HTBN [hydroxy-terminated poly(butadiene-co-acrylonitrile)] and TDI (tolylene diisocyanate) is described. The progress of the reaction and the structural changes during modification process are studied using IR spectroscopy, viscosity data, and chemical analysis (epoxy value determination). The studies support the proposition that TDI acts as a coupling agent between the epoxy and HTBN, forming a urethane linkage with the former and an oxazolidone ring with the latter. The chemical reactions that possibly take place during the modification are discussed.

Characterization of poly- and monoclonal antibodies to physalis mottle (tymo) virus

Polyclonal antibodies were raised against the Physalis mottle virus (PhMV) and its denatured coat protein (PhMV-P). Analysis of the reactivity of the polyclonal antibodies with tryptic peptides of PhMV-P in dot-blot assays revealed that many of the epitopes were common to intact virus and denatured coat protein. Five monoclonal antibodies to the intact virus were obtained using hybridoma technology. These monoclonal antibodies reacted well with the denatured coat protein. Epitope analysis suggested that probably these monoclonal antibodies recognize overlapping epitopes. This was substantiated by epitope mapping using the CNBr digest of PhMV-P in western blots. All the five monoclonals recognized the N-terminal 15 K fragment. Attempts to further delineate the specific region recognized by the monoclonals by various enzymatic cleavages resulted in the loss of reactivity in all the cases. The results indicate that these monoclonals probably recognize epitopes within the N-terminal 15 K fragment of the coat protein.

Crystal and Molecular Structure of Sclerophytin F Methyl Ether from the Soft Coral Cladiella krempfi

new cembranoid diterpene was isolated from the soft coral Ckdiella h p f ifrom Minicoy Island (India), and its structure was established by X-ray crystallography to be sclerophytin F methyl ether (21 with the R absolute configuration at all six epimeric centers,assuming a configuration similar to that of sclerophytin C. Compound 2 may be an artifact of the isolation process.

Novel photocrosslinkable liquid-crystalline polymers: poly[bis(benzylidene)] esters

A new class of photo-cross-linkable main-chain liquid crystalline polymers (PMCLCPs) containing bis(benzylidene)cycloallranone groups have been synthesized and studied for their liquid crystalline and photochemical properties. The bis(benzylidene)cycloalkanone group in the chain functions both as a mesogen and as a photoreactive center. All of the polymers exhibit a nematic mesophase. Two kinds of photoreactions, namely, photoisomerization and photo-cross-linking, operate in these polymers. Above Tu at the initial stages of irradiation, photoisomerization predominates the cross-linking, which resulta in the disruption of the chromophore aggregates. Below T8, because of the restricted mobility of the chains, only cross-linking takes place. Studies on the model compound, bis(benzylidene)cyclopentanone, confii the above observations and demonstrate further that the cross-linking proceeds by the 2r + 2r cycloaddition reaction of the bis(benzylidene)cycloallranone moieties. The cross-linking rate decreases with increase in the size of the cycloalkanone ring. Heating the solution cast polymer fii results in the ordered aggregation of the chromophores just above TI and also at the crystal to crystal transition temperature, which facilitates the phobcross-linking reactions. In the isotropic phase, the random orientation of the chromophores drastically curtails the cross-linking rata

Novel polymeric flame retardant plasticizers for poly(vinyl chloride)

Polyphosphate esters have been used as polymeric flame retardant plasticizers in poly(vinyl chloride); thermal and flammability studies were carried out to evaluate their efficiencies as fire retardants. A comparison is also made on the fire retardancy of the conventional simple phosphates with that of the polyphosphates as novel fire retardant plasticizers for PVC.

One pot synthesis of polycyclic oxygen aromatics. Part IV reaction of THP ether of 2-bromomethyl phenols

Reaction of 2-bromomethyl-1-(2′-tetrahydropyranyloxy) benzene 3a with tetrachlorocatechol(TCC) in acetone in presence of anhydrous K2CO3 resulted in the formation of diastereomeric products to which cis- & trans- 6-chloro-8-hydroxy-8-(2-oxopropyl)spiro[9H-benzo[a]xanthen- 9,2′(1′H) benzofuran]-7(8H)-one (7a & 8a) structures were assigned, along with tetrachlorocatechol ethers (5a & 6a). Similar reaction of 3a with tetrabromocatechol(TBC) gave the expected monobromo compounds 7d & 8d along with the ethers 5d & 6d. When the reaction was repeated with substrates 3b–c with TCC/TBC in ketonic solvents(acetone/methyl ethyl ketone), the corresponding compounds 5b–c to 8b–c, 5e–f to 6e–f, 7e–g & 8e–h were obtained. A suitable explanation has been given for the formation of acetonyl compound 6 in this reaction.

Reactivity of pyridinium poly(hydrogen fluoride) towards silicon tetrachloride, trichlorosilane and tris(amino)silanes

The reaction of silicon tetrachloride (SiCl4), trichlorosilane (HSiCl3) and tris(amino)silanes[(R2N)3SiH] with pyridinium poly(hydrogen fluoride) (PPHF) gives rise to hexafluorosilicatesalts in good yields. They have been characterized as pyridinium hexafluorosilicate(C5H5NH)2SiF6 (in the case of SiCl4 and HSiCl3) and the corresponding dialkyl ammoniumhexafluorosilicate (R2NH2)2SiF6 salts [for tris(amino)silanes] (where R2N=pyrrolidino,piperidino, hexamethyleneimino, morpholino, N-methylpiperazino and diethylamino). Theinteresting features of these reactions are the cleavage of Si---Cl, Si---H and Si---N bondsat room temperature by PPHF and fluorination of the silicon moiety to a hexa-coordinateddoubly charged anionic species. These compounds have been characterized by NMR (1H,29Si, 19F) and IR spectroscopy, and by chemical analysis.

Electron-beam irradiation effects on poly(ethylene-co-vinyl acetate) polymer

Poly(ethylene-co-vinyl acetate) (EVA) films were irradiated with a 1.2MeV electron beam at varied doses over the range 0-270kGy in order to investigate the modifications induced in its optical, electrical and thermal properties. It was observed that optical band gap and activation energy of EVA films decreased upon electron irradiation, whereas the transition dipole moment, oscillator strength and number of carbon atoms per cluster were found to increase upon irradiation. Further, the dielectric constant, the dielectric loss, and the ac conductivity of EVA films were found to increase with an increase in the dose of electron radiation. The result further showed that the thermal stability of EVA film samples increased upon electron irradiation.

Poly-ols Based Sol-Gel Synthesis of Zinc Oxide Thin Films

We demonstrate that the structural and optical properties of a sol-gel deposited zinc oxide thin film can be tuned by varying the composition of the sol, consisting of ethylene glycol and glycerol. A systematic study of the effect of the composition of sol on the mean grain size, thickness, and defect density of the zinc oxide film is presented. About 20% glycerol content in the sol is observed to improve the quality of the film, as evaluated by X-ray diffraction and photoluminescence studies. Thus, optimizing the composition of the sol for about 60 nm thick ZnO film using 20% glycerol resulted in the zinc oxide film that is about 80% transparent in visible spectrum, exhibiting electrical resistivity of about 18 Omega cm and field-effect mobility of 0.78 cm(2)/(V s). (C) 2010 The Electrochemical Society. DOI: 10.1149/1.3515894] All rights reserved.

Second harmonic generation in poled molecularly doped polymer films : Push-pull butadienes in poly(methyl methacrylate) and polystyrene

We report second harmonic generation in a new class of organic materials, namely donor-acceptor substituted all-trans butadienes doped in poly(methyl methacrylate) or polystyrene and oriented by corona poling at elevated temperatures. Second harmonic measurements were made at room temperature. The observed d33 coefficients are greater than those of potassium dihydrogen phosphate or 4-dimethylamino-4'-nitrostilbene doped in similar polymer matrices. Rotational diffusion coefficients estimated from the decay characteristics of the second harmonic intensity in the polymer films indicate that the polymer matrix plays a major role in stabilizing the dopants in a nonlinear optics conducive environment.

A study of the reaction of divalent transition metal chlorides with pyridinium poly(hydrogen fluoride), ppht, and the effect of potassium hydrogen fluoride on fluorination and complexation

Studies of the reaction of metal chlorides, MCl2 (M = Mn, Co, Ni, Cu, Zn) with PPHF at room temperature have shown that Mn, Co and Zn form the corresponding metal fluorides, MF2, while Ni and Cu form their dipyridine metal(II) dichloride complexes. Nickel and copper complexes further undergo fluorination and complexation by potassium hydrogen fluoride in PPHF to form KNiF3 and KCuF3.

Miscibility of Poly(aromatic acrylate)s and Methacrylates with Styrene/Acrylonitrile copolymers

Miscibilities of some poly[aromatic (meth)acrylatels namely, poly(pheny1 acrylate) (PPA), poly(pheny1 methacrylate) (PPMA), poly(benzy1 acrylate) (PBA), and poly(benzy1 methacrylate) (PBMAY polystyrene blends, have been studied through the so-called copolymer effect by incorporating acrylonitrile units in PS chains. In these systems, miscibility occurs on account of the strong repulsion between the acrylonitrile and styrene units in the copolymer. PBA and PBMA were blended with different styreneacrylonitrile (SAN) copolymers. A miscibility window has been identified for the latter system, and from these limits, the binary interaction energy density parameters (B,j.’sw) ere calculated. Using these values, the miscibilities in other homopolymer-copolymer and copolymer-copolymer systems containing benzyl methacrylate, acrylonitrile, and styrene monomer units have been predicted and subsequently verified experimentally. The miscibility window limits in poly[aromatic (meth)acrylate]s/SAN copolymer blends have been compared. PBA does not exhibit a miscibility window with SAN copolymers, which has been explained by the weak intramolecular hydrogen bonding in PBA. The miscibility window in the PBW SAN copolymer system, as observed by DSC, shows a considerable narrowing in nonradiative energy transfer (NRET) measurements, as this technique is more sensitive.

Miscibility of poly(aromatic acrylate)s and methacrylates with styrene/acrylonitrile copolymers

Miscibilities of some poly[aromatic (meth)crylate]s namely, poly(phenyl acrylate) (PPA, poly(phenyl methacrylate) (PPMA), poly(benzyl acrylate) (PBA), and poly(benzyl methacrylate) (PBMA)/polystyrene blends, have been studied through the so-called copolymer effect by incorporating acrylonitrile units in PS chains. In these systems, miscibility occurs on account of the strong repulsion between the acrylonitrile and styrene units in the copolymer. PBA and PBMA were blended with different styrene-acrylonitrile (SAN) copolymers. A miscibility window has been identified for the latter system, and from these limits, the binary interaction energy density parameters (Bij's) were calculated. Using these values, the miscibilities in other homopolymer-copolymer and copolymer-copolymer systems containing benzyl methacrylate, acrylonitrile, and styrene monomer units have been predicted and subsequently verified experimentally. The miscibility window limits in poly[aromatic (meth)acrylate]s/SAN copolymer blends have been compared. PBA does not exhibit a miscibility window with SAN copolymers, which has been explained by the weak intramolecular hydrogen bonding in PBA. The miscibility window in the PBMA/SAN copolymer system, as observed by DSC, shows a considerable narrowing in nonradiative energy transfer (NRET) measurements, as this technique is more sensitive.

Photoinduced electron transfer in zinc porphyrin-crown ether supramolecule with Eu3+ electron acceptor in crown void

Photoinduced electron transfer (ET) reactions in the zinc porphyrin-crown ether (ZnPCE) supramolecule, in which one crown ether moiety containing Eu3+ as electron acceptor is covalently linked to zinc porphyrin (ZnP), were studied by flash photolysis. In methanol solutions, highly efficient charge separation occurs via intramolecular ET from (ZnP)-Zn-3 to Eu3+ encapsulated in the crown ether void (k(1) = (3 +/- 1) X 10(3) s(-1)) and intramolecular ET from 3ZnP to uncomplexed Eu2+ (k(2) = (2.5 +/- 0.5) X 10(3) s(-1)). Intermolecular ET from Eu2+ escaped from the crown ether void to ZnP.+ (k(tau) = (4.3 +/- 0.7) X 10(8) M(-1) s(-1)) seems to be the main pathway of charge recombination.