Poly(Alpha-olefins)

This paper describes a new method to enhance the heat-transfer property of a single-phase liquid by adding encapsulated phase-change nanoparticles (nano-PCMs), which absorb thermal energy during solid-liquid phase changes. Silica-encapsulated indium nanoparticles and polymer-encapsulated paraffin (wax) nanoparticles have been made using colloid method, and suspended into poly-alpha-olefin (PAO) and water for potential high- and low-temperature applications, respectively. The shells prevent leakage and agglomeration of molten phase-change materials, and enhance the dielectric properties of indium nanoparticles...

Compounds [Cp*(2)M(2)O(5)] (M = Mo, 1; W, 2) are efficient pre-catalysts for cyclooctene (COE) epoxidation by aqueous H(2)O(2) in acetonitrile/toluene. The reaction is quantitative, selective and takes place approximately 50 times faster for the W system (k(obs) = 4.32(9)x10(-4) s(-1) at 55 degrees C and 3x10(-3) M concentration for the dinuclear complex, vs. 1.06(7)x10(-5) s(-1) for the Mo system). The rate law is first order in catalyst and COE substrate (k = 0.138(7) M(-1) s(-1) for the W system at 55 degrees C), whereas increasing the concentration of H(2)O(2) slows down the reaction because of an inhibiting effect of the greater amount of water...

A DFT analysis of the epoxidation of C(2)H(4) by H(2)O(2) and MeOOH (as models of tert-butylhydroperoxide, TBHP) catalyzed by [Cp*MoO(2)Cl] (1) in CHCl(3) and by [Cp*MoO(2)(H(2)O)](+) in water is presented (Cp*=pentamethylcyclopentadienyl). The calculations were performed both in the gas phase and in solution with the use of the conductor-like polarizable continuum model (CPCM). A low-energy pathway has been identified, which starts with the activation of ROOH (R=H or Me) to form a hydro/alkylperoxido derivative, [Cp*MoO(OH)(OOR)Cl] or [Cp*MoO(OH)(OOR)](+) with barriers of 24...

The entropy theory of glass formation, which has previously been developed to describe general classes of polymeric glass-forming liquids, is extended here to model the thermodynamic and dynamic properties of poly(alpha-olefins). By combining this thermodynamic theory with the Adam-Gibbs model (which relates the configurational entropy to the rate of structural relaxation), we provide systematic computations for all four characteristic temperatures (T(A), T(c), T(g), T(0)), governing the position and breadth of the glass transition, and the fragility parameters (D,m) describing the strength of the temperature dependence of the structural relaxation time, where T(A) is the temperature below which the relaxation is non-Arrhenius, T(c) is the crossover or empirical mode-coupling temperature, T(g) is the glass transition temperature, and T(0) is the temperature at which the extrapolated relaxation time diverges...

The elastic properties of materials under high pressure are relevant to the understanding and performance of many systems of current interest, for example, in geology and tribology. Of particular interest is the origin of the dramatic increase in modulus with increasing pressure, a response which is also called "smart materials behavior." In this context, simple phosphate-containing materials have been studied experimentally and theoretically, and the origins of this behavior have been associated with factors such as coordination of the cations and changes in the degree of polymerization and hydrogenation of the phosphate units...

Catalysts contribute to the efficient production of chemicals and materials in almost all processes in the chemical industry. The polyolefin industry is one prominent example of the importance of catalysts. The discovery of Ziegler-Natta catalysts in the 1950s resulted in the production of high-density polyethylenes (PEs) and isotactic polypropylenes (iPPs). Since then, further catalyst development has led to the production of a new series of polyolefins, including linear low-density PEs, amorphous ethylene/1-butene copolymers, ethylene/propylene/diene elastomers, and syndiotactic PPs (sPPs)...

Multiple facet supported alumina nanowires are produced very efficiently in a very short time via high field anodization; upon modification with perfluorosilane, the surface becomes super-repellent towards a broad range of liquids, which includes (salted) water, water emulsion, common organic liquids like glycerol and alkanes, and a variety of lubrication oils including ionic liquids, poly(alpha-olefin), polydimethylsiloxane oils etc.

A simple batch vacuum evaporation process for the treatment of several oil-in-water (O/W) emulsions is reported. The experiments were carried out with waste emulsions from an industrial copper rolling process and with model emulsions prepared in the laboratory. No detailed information on the formulation of the industrial waste O/W emulsions was available. Several model emulsions were formulated using the same base oil (an 85-15% (w/w) mixture of a synthetic poly-alpha-olefin and a trimethylol propane trioleate ester, respectively) and one of the three following surfactants: Brij-76 (polyethylene glycol octadecyl ether, non-ionic), CTAB (hexadecyltrimethyl ammonium bromide, cationic), and Oleth-10 (glycolic acid ethoxylate oleyl ether, anionic)...

The synthesis of novel alternating polyketones bearing pendent bioactive moieties is presented. These materials were prepared by palladium catalyzed coordination polymerization of carbon monoxide and alpha-olefins substituted with protected tyrosine or with dipeptide sequences such as tyrosine-glycine, tyrosine-alanine, and tyrosine-valine. Copolymerization experiments of CO with monomers containing vitamin E or testosterone were also successfully performed under mild reaction conditions. The dicationic Pd (II) bis(phoshine) complex [Pd(dppp)(NCCH(3))(2)](BF(4))(2) was used as catalyst precursor giving rise to macromolecules with well-defined structures...

This paper reports that (alpha-diimine)PdMe+ catalyzes the copolymerization of olefins and silyl vinyl ethers. The reactions of (alpha-diimine)PdMe+ (alpha-diimine = (2,6-iPr2-C6H3)N=CMe-CMe=N(2,6-iPr2-C6H3)) with excess vinyl ethers CH2=CHOR (1a-d: R = tBu (a), SiMe3 (b), SiPh3 (c), Ph (d)) in CH2Cl2 at 20 degrees C afford polymers for 1a (rapidly) and 1b (slowly) but not for 1c or 1d. The structures of poly(1a,b) indicate a cationic polymerization mechanism. The reaction of (alpha-diimine)PdMe+ with 1-2 equiv of 1a-d proceeds by sequential C=C pi-complexation to form (alpha-diimine)PdMe(CH2=CHOR)+ (2a-d), 1,2 insertion to form (alpha-diimine)Pd(CH2CHMeOR)+ (3a-d), reversible isomerization to (alpha-diimine)Pd(CMe2OR)+ (4a-d), beta-OR elimination to generate (alpha-diimine)Pd(OR)(CH2=CHMe)+ (not observed), and allylic C-H activation to yield (alpha-diimine)Pd(eta3-C3H5)+ (5) and ROH...

A series of anomerically pure 1-O-formyl glycosides 1 was prepared and converted into the corresponding 1-O-vinyl glycosides 2 by Tebbe olefination. The unsubstituted vinyl glycosides were obtained as anomerically pure compounds in good yields, and the method of preparation was compatible with the presence of a variety of functional groups. Remarkably, the anomeric formate group was regioselectively converted into the corresponding olefin in the presence of acetate and benzoate protecting groups. With the perspective to use the 1-O-vinyl glycosides as monomers for the preparation of glycosylated poly(vinyl alcohol) derivatives with controlled tacticity, their scope as chiral auxiliaries for a stereodifferentiation in addition reactions to the olefin function was investigated by using the [2+2] cycloaddition to dichloroketene as a model reaction...

TSI Inc. (Shoreview, MN) has introduced three new water-based condensation particle counters (WCPCS) that were designed to detect airborne particles larger than 2.5 nm (model 3786), 5 nm (model 3785), and either 10 or 20 nm (model 3782). These WCPCs are well suited for real-time, environmental monitoring of number concentration of airborne ultrafine particles. Their unique design incorporates the use of water as the working fluid instead of alcohol. Water is odor free, readily available, and eliminates the problem of water condensation and absorption into alcohol working fluids during operation in humid environments...

In this work, the elongational flow behavior of aqueous solutions of poly(ethylene oxide) (PEO) was studied in the presence of sulfonated surfactants. The technique of opposed-jets flow was used to generate an elongational flow field in which pressure drops were measured as a function of strain rates. The surfactants used were sodium dodecyl benzene sulfonate (SDBS) and an alpha-olefin sulfonate (AOS). Solutions of PEO and other flexible polymers exhibit extension thickening in opposed-jets flow due to the formation of transient networks of entangled molecules...

A series of 6.5.5 spiro bicyclic lactam scaffolds were synthesized from pipecolic acid in a sequence of reactions that was initiated with the alpha-allylation of tert-butoxycarbonyl pipecolic acid. Oxidative cleavage of the olefin to give an aldehyde followed by condensation with D-cysteine methyl ester gave a mixture of pipecolyl thiazolidines. Cyclization of the pipecolyl thiazolidines with Mukaiyama's reagent yielded the spiro bicyclic lactams 4a-d. Epimerization of the 7'a bridgehead carbon under acidic conditions was observed for those spiro bicyclic lactam scaffolds with an S stereochemistry at this position...

The structurally unique, sterically expanded eta1-fluorenyl-eta1-amido single-site precatalyst, Me2Si(eta1-N-tBu)(eta1-C29H36)ZrCl2.OEt2 (3), upon activation with methylaluminoxane (MAO), is remarkably active and constitutes the most syndioselective alpha-olefin polymerization catalyst system yet reported. 3/MAO affords as-prepared syndiotactic polypropylene with [rrrr] > 99% and unprecedented melting temperatures for the unannealed (165 degrees C) and annealed (174 degrees C) polymers. The activity of this system is 4 times that of the prototypical syndioselective catalyst Me2C(eta5-C5H4)(eta5-C13H8)ZrCl2/MAO...

Sugar-substituted epoxides 5-8 were synthesized by asymmetric epoxidation (in CH(2)Cl(2)/water) of alpha-olefins having neighboring sugars (1-4) by use of an achiral oxidant (MCPBA), in which the sugar moiety acted as a chiral template. The diastereoselectivities depend on the methylene spacer between vinyl group and carbohydrate derivatives. The methylene spacer between sugar and vinyl groups influenced the diastereoselectvity. In the case of epoxidation of 4 at 27 degrees C for 24 h, the diastereoselectivity was the highest (99/1)...

Properties of polymer alloys comprising poly(lactic acid) and Nodax copolymers are investigated. Nodax is a family of bacterially produced polyhydroxyalkanoate (PHA) copolymers comprising 3-hydroxybutyrate (3HB) and other 3-hydroxyalkanoate (3HA) units with side groups greater than or equal to three carbon units. The incorporation of 3HA units with medium-chain-length (mcl) side groups effectively lowers the crystallinity and the melt temperature, Tm, of this class of PHA copolymers, in a manner similar to that of alpha olefins controlling the properties of linear low density polyethylene...

This contribution reports the discovery and application of phenoxy-imine-based catalysts for olefin polymerization. Ligand-oriented catalyst design research has led to the discovery of remarkably active ethylene polymerization catalysts (FI Catalysts), which are based on electronically flexible phenoxy-imine chelate ligands combined with early transition metals. Upon activation with appropriate cocatalysts, FI Catalysts can exhibit unique polymerization catalysis (e.g., precise control of product molecular weights, highly isospecific and syndiospecific propylene polymerization, regio-irregular polymerization of higher alpha-olefins, highly controlled living polymerization of both ethylene and propylene at elevated temperatures, and precise control over polymer morphology) and thus provide extraordinary opportunities for the syntheses of value-added polymers with distinctive architectural characteristics...

The absorbance and fluorescence spectra of Nile Red (NR) were examined in a series of nonpolar solvents comprising linear alkanes and a range of poly alpha olefins (PAO). These solvents span a 1000-fold range in viscosity and possess very similar dielectric constants and refractive index properties. A high-energy double peak with vibronic structure is observed in both fluorescence and absorbance spectra, possibly indicating that a locally excited (LE) state is accessed in these solvents. In addition, a red shift in peak position is observed with increasing refractive index; however, it is unaccompanied by any changes in Stokes shift...

A series of enantiopure C1-symmetric metallocenes, [(SiMe2)2[eta5-C5H(CHMe2)2][eta5-C5H2((S)-CHMeCMe3)]]ZrCl2, (S)-2, [(SiMe2)2[eta5-C5H(CHEt2)2][eta5-C5H2((S)-CHMeCMe3)]]ZrCl2, (S)-6, and [(SiMe2)2[eta5-C5HCy2][eta5-C5H2((S)-CHMeCMe3)]]ZrCl2, (S)-7 (Cy = cyclohexyl), zirconocene dichlorides that have an enantiopure methylneopentyl substituent on the "upper" cyclopentadienyl ligand, and diastereomerically pure precatalysts, [(SiMe2)2[eta5-C5H((S)-CHMeCy)(CHMe2)][eta5-C5H3]]ZrCl2, (S)-8a and (S)-8b, which have an enantiopure, 1-cyclohexylethyl substituent on the "lower" cyclopentadienyl ligand, has been synthesized for use in the polymerization of chiral alpha-olefins...