A DFT study of propylene polymerization using neutral salicyladiminato nickel(II) and palladium(II) as catalysts

Propylene polymerization using salicyladiminato metal catalalysts has been studied using density functional theory at the B3LYP/LANL2DZ level. In particular, the effects on the reaction mechanisms of changing the metal from Pd(II) to Ni(II) have been investigated. While the reaction mechanisms involving the salicyladiminato Ni(II) catalyst have been found to be similar to those established previously for the salicyladiminato Pd(II) catalyst, the nickel catalyst was found to differentiate the trans-O intermediate from the trans-.N intermediate with an energy difference of 46.63 U mol(-1) significantly more than the palladium catalyst for which the energy difference was calculated as 35.82 kJ mol(-1). The energy difference between the trans-O configuration and the trans-N configuration is decreased significantly when combining a molecule of propylene with the catalyst. For the Ni catalyst, the trans-O isomer is more stable than the trans-N isomer to a greater extent than for Pd, so that the insertion of propylene from 20 is relatively less favoured for Ni than for Pd. It is predicted that the mechanism of isomerization from 20 to 2N through a rotational transition state TS2O2N is more appropriate for the Ni catalyst system. The palladium system shows a larger preference for pi-coordination than its nickel counterpart, although the latter possesses a lower reaction barrier. It was found that the occupation of the trans-O position in the asymmetric salicyladiminato catalyst is also more favored by the alkene as it is by the alkyl so that insertion of the alkene may always start from a particular configuration so that specific products are obtained. (c) 2005 Elsevier B.V. All rights reserved.

Photopolymerization of Pluronic F127 diacrylate: a colloid-templated polymerization

Pluronic F127 diacrylate (F127DA) is a bifunctional acrylate and as such it should in principle produce macroscopically cross-linked materials; however, its photopolymerization in water does not lead to 3D-extended hydrogels. The main species present after photopolymerization appear to be cross-linked micelles, which indicates that the micellar morphology of F127DA has a template effect on the polymerization. The structural analogy causes the physical state of precursor and polymerized materials to be very similar for a wide range of concentrations (5–25% wt) and temperatures (10–37 °C). Also the long-range morphology of F127DA appears to have a template effect: samples photopolymerized in a micellar gel state and redispersed at high concentration (25% wt) show a long-range organization that depended on the concentration and therefore on the order of the precursor.

Composition and cure temperature: The influence on properties of final flexible PU cold cure foam parts

Foams are cellular structures, produced by gas bubbles formed during the polyurethane polymerization mixture. Flexible PU foams meet the following two criteria: have a limited resistance to an applied load, being both permeable to air and reversibly deformable. There are two main types of flexible foams, hot and cold cure foams differing in composition and processing temperatures. The hot cure foams are widely applied and represent the main composition of actual foams, while cold cure foams present several processing and property advantages, e.g, faster demoulding time, better humid aging properties and more versatility, as hardness variation with index changes are greater than with hot cure foams. The processing of cold cure foams also is attractive due to the low energy consumption (mould temperature from 30 degrees to 65 degrees C) comparatively to hot cure foams (mould temperature from 30 degrees to 250 degrees C). Another advantage is the high variety of soft materials for low temperature processing moulds. Cold cure foams are diphenylmethane diisocyanate (MDI) based while hot cure foams are toluene diisocyanate (TDI) based. This study is concerned with Viscoelastic flexible foams MDI based for medical applications. Differential Scanning Calorimetry (DSC) was used to characterize the cure kinetics and Dynamical Mechanical Analisys to collect mechanical data. The data obtained from these two experimental procedures were analyzed and associated to establish processing/properties/operation conditions relationships. These maps for the selection of optimized processing/properties/operation conditions are important to achieve better final part properties at lower costs and lead times.

Laurentide ice streaming on the Canadian Shield: A conflict with the soft-bedded ice stream paradigm?

Elucidating the controls on the location and vigor of ice streams is crucial to understanding the processes that lead to fast disintegration of ice flows and ice sheets. In the former North American Laurentide ice sheet, ice stream occurrence appears to have been governed by topographic troughs or areas of soft-sediment geology. This paper reports robust evidence of a major paleo-ice stream over the northwestern Canadian Shield, an area previously assumed to be incompatible with fast ice flow because of the low relief and relatively hard bedrock. A coherent pattern of subglacial bedforms (drumlins and megascalle glacial lineations) demarcates the ice stream flow set, which exhibits a convergent onset zone, a narrow main trunk with abrupt lateral margins, and a lobate terminus. Variations in bedform elongation ratio within the flow set match theoretical expectations of ice velocity. In the center of the ice stream, extremely parallel megascalle glacial lineations tens of kilometers long with elongation ratios in excess of 40:1 attest to a single episode of rapid ice flow. We conclude that while bed properties are likely to be influential in determining the occurrence and vigor of ice streams, contrary to established views, widespread soft-bed geology is not an essential requirement for those ice streams without topographic control. We speculate that the ice stream acted as a release valve on ice-sheet mass balance and was initiated by the presence of a proglacial lake that destabilized the ice-sheet margin and propagated fast ice flow through a series of thermomechanical feedbacks involving ice flow and temperature.

Soft topographic map for clustering and classification of bacteria

In this work a new method for clustering and building a topographic representation of a bacteria taxonomy is presented. The method is based on the analysis of stable parts of the genome, the so-called “housekeeping genes”. The proposed method generates topographic maps of the bacteria taxonomy, where relations among different type strains can be visually inspected and verified. Two well known DNA alignement algorithms are applied to the genomic sequences. Topographic maps are optimized to represent the similarity among the sequences according to their evolutionary distances. The experimental analysis is carried out on 147 type strains of the Gammaprotebacteria class by means of the 16S rRNA housekeeping gene. Complete sequences of the gene have been retrieved from the NCBI public database. In the experimental tests the maps show clusters of homologous type strains and present some singular cases potentially due to incorrect classification or erroneous annotations in the database.

Dual carrier modulation soft demapper

An Orthogonal Frequency Division Multiplexing (OFDM) communication system with a transmitter and a receiver. The transmitter is arranged to transmit channel estimation sequences on each of a plurality of band groups, or bands, and to transmit data on each of the band groups or bands. The receiver is arranged to receive the channel estimation sequences for each band group or band to calculate channel state information from each of the channel estimation sequences transmitted on that band group or band and to form an average channel state information. The receiver receives the transmitted data, transforms the received data into the frequency domain, equalizes the received data using the channel state information, demaps the equalized data to re-construct the received data as soft bits and modifies the soft bits using the averaged channel state information.

Development of a capillary electrophoresis method for the simultaneous analysis of artificial sweeteners, preservatives and colours in soft drinks

A rapid capillary electrophoresis method was developed simultaneously to determine artificial sweeteners, preservatives and colours used as additives in carbonated soft drinks. Resolution between all additives occurring together in soft drinks was successfully achieved within a 15-min run-time by employing the micellar electrokinetic chromatography mode with a 20 mM carbonate buffer at pH 9.5 as the aqueous phase and 62 mM sodium dodecyl sulfate as the micellar phase. By using a diode-array detector to monitor the UV-visible range (190-600 nm), the identity of sample components, suggested by migration time, could be confirmed by spectral matching relative to standards.

A novel approach to processing high-performance polymers that exploits entropically driven ring-opening polymerization

Blends of the poly(ether sulfone) derived from 4,4'-biphenol and 4,4'-dichlorodiphenylsulfone (Radel-R(TM)) with its homologous macrocyclic oligomers show greatly lowered melt viscosities relative to that of the parent polymer, potentially enabling more facile production and fabrication of fiber-reinforced composite materials. The macrocycles can then undergo entropically driven ring-opening polymerization in situ. The required blends can be obtained easily in one step, by carrying out polycondensations at concentrations lower than those usually used for polymer synthesis.

Synthesis of a catechol-based poly(ether ether ketone) ("o-PEEK") by classical step-growth polymerization and by entropically driven ring-opening polymerization of macrocyclic oligomers

An amorphous, catechol-based analogue of PEEK ("o-PEEK") has been prepared by a classical step-growth polymerization reaction between catechol and 4,4'-difluorobenzophenone and shown to be readily soluble in a range of organic solvents. Copolymers with p-PEEK have been investigated, including an amorphous 50: 50 composition and a semicrystalline though still organic-soluble material comprising 70% p-PEEK. o-PEEK has also been obtained by entropy-driven ring-opening polymerization of the macrocyclic oligomers (MCO's) formed by cyclo-condensation of catechol with 4,4'-difluorobenzophenone under pseudo-high-dilution conditions. The principal products of this latter reaction were the cyclic dimer 3a (20 wt %), cyclic trimer 3b (16%) cyclic tetramer 3c (14%), cyclic pentamer 3d (13%) and cyclic hexamer 3e (12%). Macrocycles 3a-c were isolated as pure compounds by gradient column chromatography, and the structures of the cyclic dimer 3a and cyclic tetramer 3c were analyzed by single-crystal X-ray diffraction. A mixture of MCO's, 3, of similar composition, was obtained by cyclodepolymerization of high molar mass o-PEEK in dilute soluion.

Ring-chain interconversion in high-performance polymer systems. 3. Cyclodepolymerization of poly(m-phenylene isophthalamide) (Nomex) and entropically driven ring-opening polymerization of the macrocyclic oligomers so produced

A homologous series of macrocyclic oligoamides has been prepared in high yield by reaction of isophthaloyl chloride with m-phenylenediamine under pseudo-high-dilution conditions. The products were characterized by infrared and H-1 NMR spectroscopies, matrix assisted laser desorption-ionization time-of-flight mass spectrometry, and gel permeation chromatography (GPC). A series of linear oligomers was prepared for comparison. The macrocycles ranged in size from the cyclic trimer up to at least the cyclic nonamer (90 ring atoms). The same homologous series of macrocyclic oligomers was prepared in high yield by the cyclodepolymerization of poly(m-phenylene isophthalamide) (Nomex). Cyclodepolymerization was best achieved by treating a 1% w/v solution of the polymer in dimethyl sulfoxide containing calcium chloride or lithium chloride with 3-4 mol % of sodium hydride or the sodium salt of benzanilide at 150 degreesC for 70 h. Treatment of a concentrated solution of the macrocyclic oligomers (25% w/v) with 4 mol % of sodium hydride or the sodium salt of benzanilide in a solution of lithium chloride in dimethyl sulfoxide at 170 degreesC for 6 h resulted in efficient entropically driven ring-opening polymerizations to give poly(m-phenylene isophthalamide), characterized by infrared and H-1 NMR spectroscopies and by GPC. The molecular weights obtained were comparable with those of the commercial polymer.

Enthalpy-driven ring-opening polymerization of highly strained macrocyclic biaryl-ether-ketones

Highly strained macrocyclic ether-ketones obtained by nickel-catalyzed cyclization of linear precursor oligomers undergo ring-opening polyinerization via ether exchange in the presence of nucleophilic initiators such as fluoride or phenoxide anions. Strain enthapies of these macrocycles, from DSC analyses of their exothermic ring-opening polymerization are in the range 50-90 kJ mol(-1). Melt-phase polymerization generally affords slightly cross-linked materials, but solution-phase polymerization at high macrocycle concentrations gives fully soluble, high molar mass polymers with inherent viscosities of up to 1.78 dL g(-1). Sequence-analysis of the resulting polymers by C-13 NMR shows that alternating or random monomer sequences may be obtained, depending on whether one or both aromatic rings adjacent to the ether linkages are activated toward nucleophilic attack.

Synthesis of strained macrocyclic biaryls for enthalpy-driven ring-opening polymerization

Polymerizable macrocyclic biarylene-ether-ketones and biarylene-ether-sulfones are accessible from linear, bis(chloro)-terminated oligomers via nickel-catalyzed, intramolecular coupling under pseudo-high-dilution conditions. Single-crystal X-ray analyses of the resulting cyclo-oligomers reveal extremely distorted and highly strained geometries, with 4,4 '-biphenylene units showing deviations of up to 70 degrees from linearity.

Spontaneous ring-opening polymerization of macrocyclic aromatic thioether ketones under transient high-temperature conditions

Spontaneous ring-opening polymerization of macrocyclic aromatic thioether ketones [-1,4-SC6H4CO-C6H4-](n) (n = 3 and 4), in which the thioether linkages are para to the ketone, occurs during rapid, transient heating to 480degreesC, to afford a soluble, semi-crystalline poly(thioether ketone) of high molar mass (eta(inh) > 1.0 dL . g(-1)). Corresponding macrocyclic ether ketone, and a macrocyclic thioether ether ketone in which the thioether linkage is para to the ether rather than to the ketone, show no evidence of polymerization under analogous conditions.