New telechelic polymers and sequential copolymers by polyfunctional initiator-transfer agents (inifers)

Summary Novel oxycarbonyl isocyanate telechelic polyisobutylenes have been prepared by conversion of hydroxylterminated polyisobutylenes with N-chlorocarbonyl isocyanate. This reaction is free from side-reactions and provides highly reactive isocyanate-terminated polyisobutylene prepolymers. Conversion of these prepolymers with glycol, urea, pentaerythritol, and polyethylene glycol led to linear chain extension, crosslinking, and multiblock copolymer formation, respectively.     

Silphinene Sesquiterpenes as Model Insect Antifeedants

Silphinene sesquiterpenes are established chrysomelid antifeedants. In this work, nine silphinene analogs, 11-acetoxy-5-angeloyloxysilphinen-3-one (1), 11-acetoxy-5-tigloyloxysilphinen-3-one (2), 11-acetoxy-5-iso- butyryloxysilphinen-3-one (3), 11-hydroxy-5-angeloyloxysilphinen-3-one (4), 11,5-dihydroxysilphinen-3-one (5), 11,5-diacetoxysilphinen-3-one (6), 5,11-diisobutyryloxysilphinen-3-one (7), silphinen-3,5,11-trione (8), and O-methyl-5-epicantabrenolic acid methyl ester (10), and a presilphiperfolane sesquiterpene (9) were tested against several divergent insect species, including the lepidopteran Spodoptera littoralis, the chrysomelid Leptinotarsa decemlineata, and five aphid species, and their antifeedant effects were compared with those of picrotoxinin, a GABA-antagonist, and thymol, an allosteric modulator for insect GABA receptors. All insects tested responded to at least one silphinene analog and/or GABA antagonist. Compound 3 and thymol were effective antifeedants against all species tested except S. littoralis, with varying potencies according to their feeding ecologies. The toxicity of these compounds was species-dependent and did not correlate with their antifeedant effect.     

Living carbocationic polymerization

Summary The living synthesis of ,-di-tert.-chloropolyisobutylene ( ^t -Cl-telechelic PIB) has been accomplished by the use of the sterically hindered bifunctional initiator 1,3-di-(2-methoxy-2-propyl)-5-tert.-butylbenzene (tBu-m-DiCuOMe) in conjunction with BC1₃ coinitiator in CH₃Cl or CH₂Cl₂ diluents at –30°C and –10°C. The living nature of the polymerizations was demonstrated by linear ¯M_n versus W_PIB (g of PIB formed) plots starting at the origin and horizontal N (number of PIB moles) versus W_PIB plots. The molecular weight distributions are narrow (¯M_W/¯M_n < 2.0) and tend to decrease with increasing molecular weights. Number average end functionalities have been quantitated and found to be ¯F_n = 2.0±0.1.     

On-line studies and computer simulation of the melt spinning of nylon-66 filaments

A mathematical model was developed to describe the high-speed melt-spinning behavior crystallizable polymers. This model included the effects of acceleration, gravity, and air friction on the kinematics of the process; temperature and molecular orientation on the crystallization kinetics of the polymer; and temperature, molecular weight, and crystallinity on the elongational viscosity of the material. Experimental on-line diameter, birefringence, and temperature profiles were obtained for a 12,000 Mn nylon-66 at 2.5 g/min spun at take-up speeds ranging from 2800 to 6600 m/min. These profiles were qualitatively and reasonably quantitatively in agreement with the predicted profiles. They indicated that orientation induced crystallization occurs at spinning speeds greater than 4000 m/min. The experimental diameter and birefringence profiles were compared to those predicted by the model using Avrami indices of 3, 2, and 1. There was a small increase in the crystalline index at the lower speeds with decreasing index. The effect of the strain hardening was more significant at the higher speeds, this being shown by decreasing the exponent in the relationship for the crystallinity on the elongational viscosity. The model developed in this study indicates that high spinning speeds provide the high stress environment that increases the molecular orientation within the fiber. It is this higher molecular orientation that is the driving force for rapid crystallization on the spinline. This rapid crystallization causes a strain hardening, preventing any further drawdown in the fiber diameter and an abrupt rise in the birefringence. This behavior closely corresponds to the observed spinline profiles.     

The influence of resin characteristics on the high speed melt spinning of isotactic polypropylene. II. On-line studies of diameter,birefringence, and temperature profiles

An investigation was carried out of the high speed melt spinning of three polypropylene resins with melt flow indices of 12, 35, and 300. On-line measurements were made of diameter, birefringence, and temperature as a function of distance from the spinneret for a range of spinning conditions for each polymer. A plateau (decrease of cooling rate) in the temperature profile was associated with the occurrence of crystallization in the spinline. The position of this plateau correlated with a rapid rise in the birefringence profile and a rapid decrease in the rate of drawdown in the diameter profile. The temperature and birefringence profiles were used to determine the temperature and position on the spinline at which the onset of crystallization occurred. It was found that the position and temperature of crystallization onset varied considerably with changes in take-up velocity, extrusion temperature, and resin melt index (weight average molecular weight). The crystallization onset occurred nearer the spinneret and at higher temperatures with (1) an increase of take-up velocity, (2) a decrease of extrusion temperature, or (3) a decrease of resin melt flow index. An analysis was carried out to estimate the rate of stress development with distance along the spinline; the results were also used to estimate the stress at the onset of crystallization for each spinning condition. It was concluded that the observed behavior could be attributed to the role of spinline stress in producing molecular orientation and consequent increase of crystallization rate.     

New phospholipid fatty acids from the marine spongeCinachyrella alloclada uliczka

The fatty acid composition of phospholipids from the Senegalese spongeCinachyrella alloclada was examined. Two new fatty acids not hitherto found in nature, namely 10,13-octadecadienoic acid and 16-tricosenoic acid, were identified. 8-Hexadecenoic, 13-nonadecenoic and 5,9,13-trimethyltretradecanoic fatty acids were also found for the first time in sponges. The latter compound (1.4% of the total fatty acid mixture), an isoprenoid fatty acid, accompanies the major fatty acid 4,8,12-trimethyltridecanoic acid (19.7%). The monomethyl branched fatty acids (22%) identified include 23-methylpentacosanoic acid (anteiso-26∶0), not previously observed in sponged. The major long-chain fatty acids encountered were the known 17-tetracosenoic 19-heptacosadienoic and 5,9,23-tricontatrienoic acid. Some sixty fatty acids were identified as methyl esters andN-acyl pyrrolidides by gas chromatography and gas chromatography/mass spectrometry.     

Effect of Precursor and Solvent on Morphology of Zirconia Nanoparticles Produced by Combustion Aerosol Synthesis

Zirconia nanoparticles were synthesized using a flame-based system involving spray droplet combustion of different precursor solutions. The characteristics of the feed were varied by varying the precursor compound, precursor concentration, and solvent type, and by using droplets of different mean sizes. When large droplets were used, agglomerated particles were formed when an organometallic precursor was used and large cenospheric particles were produced when an inorganic precursor was used. Reduction of the droplet size to a number-mean droplet diameter of 3.2 μm resulted in the production of solid spherical particles regardless of the precursor type. When an inertial impactor was used to eliminate droplets larger than 2.3 μm, the large particles in the final product were eliminated and uniformly sized solid zirconia particles having a smaller mean size were produced. The final particle size did not vary with the concentration of the precursor, indicating that multiple ceramic particles resulted from each precursor-containing droplet.     

Reaction of pyritic sulphur in coal with lime and calcined dolomite during the coking process

Various reactions occur between pyrite (FeS₂) in coal and CaO to form CaS when a finely pulverized intimate mixture of coal and CaO is coked at 900 °C in an inert atmosphere. The effectiveness of lime and calcined dolomite (CaO.MgO) in promoting this reaction has been evaluated; calcined dolomite is somewhat more effective than lime over coal/ oxide weight ratios from 2.8 to 14. The degree of conversion of pyrite to calcium sulphide at a coal/calcined dolomite weight ratio of 7 has been determined as a function of time at 900 °C; coking time in excess of 2.5 h does not have a significant effect. It has been shown that the total sulphur lost on coking coal/lime mixtures decreases and the percentage of FeS, originating from the dissociation of pyrite, converted to CaS increases as the amount of lime added increases. But although the total sulphur content of coke produced in the presence of CaO is then higher than when the coal is coked without lime, the pyritic sulphur has been converted to CaS which is more amenable to chemical conversion to H₂S. A method is outlined for determining CaS in the coked mixture in the presence of FeS.     

Characterization of the adipose tissue atrophy induced by peroxisome proliferators in mice

In the present study, we characterized the effects of peroxisome proliferators (PP) on adipose tissue in mice. Treatment with potent PP, such as perfluorooctanoic acid (PFOA), 2-methyl-2-(p(1,2,3,4-tetrahydroxy-naphthyl)-phenoxy)propionic acid, (4-chloro-6-(2,3-xylidino)2-pyrimidinylthio) acetic acid, and di(2-ethylhexyl)phthalate, caused dramatic decreases in adipose tissue weight, whereas the moderately potent PP, acetylsalicylic acid, had a relatively weak effect. This decrease in weight reflects a loss of fat from adipocytes rather than a loss of cells, as demonstrated by constant DNA content. The dose-dependency and time-course experiments indicate that peroxisome proliferation occurs simultaneously with or prior to adipose tissue atrophy. Thus, hepatic peroxisome proliferation might result in the increased mobilization of lipids and lipid utilization in liver. The enhanced adipose tissue hormonesensitive lipase (HSL) activity and down-regulated lipoprotein lipase (LPL) activity observed upon PP treatment might, at least in part, explain the loss of fat via increase FA release from adipocytes and/or decreased FA uptake from the circulation, respectively. In addition, the possible involvement of the increased tumor necrosis factor α expression found upon PFOA treatment in reducing the insulin sensitivity of adipose tissue and thereby altering LPL and HSL activities is discussed.     

A vibrational study of the activation sequence of C–H and C–C bonds of isobutene and 1-butene on Mo(110) and (4 × 4)-C/Mo(110) surfaces

The thermal decomposition pathways of isobutene and 1-butene on both Mo(110) and 4 × 4-C/Mo(110) surfaces have been studied using high-resolution electron energy loss spectroscopy (HREELS) in order to highlight the substantially different activities of these two surfaces towards the cleavage of C–H and C–C bonds. On clean Mo(110), the CH₂ group of isobutene decomposes upon heating to 150 K, producing either a /-bonded isobutenylidene [(CH₃)₂CCH] species or a 1,1-di-/-bonded isobutenyl [(CH₃)₂CC] species. Upon further heating, extensive C–H bond scission occurs to form hydrocarbon fragments which do not contain CH₃ or CH₂ groups, but appear to have largely intact carbon skeletons. By contrast, isobutene is molecularly adsorbed on the carbide-modified surface at 150 K. Further heating produces isobutylidyne [(CH₃)₂HCC] by 300 K, which subsequently decomposes via C–C bond scission to generate surface methyl groups. The different activation sequence of the C–H and C–C bonds of isobutene on clean and carbide-modified Mo(110) surfaces is also qualitatively confirmed by comparative studies of 1-butene on the two surfaces.