Radical copolymerization of 2‐trifluoromethylacrylic monomers. II. Kinetics,monomer reactivities,and penultimate effect in their copolymerization with norbornenes and vinyl ethers

Radical copolymerizations of electron‐deficient 2‐trifluoromethylacrylic (TFMA) monomers, such as 2‐trifluoromethylacrylic acid and t‐butyl 2‐trifluoromethylacrylate (TBTFMA), with electron‐rich norbornene derivatives and vinyl ethers with 2,2′‐azobisisobutyronitrile as the initiator were investigated in detail through the analysis of the kinetics in situ with ¹H NMR and through the determination of the monomer reactivity ratios. The norbornene derivatives used in this study included bicyclo[2.2.1]hept‐2‐ene (norbornene) and 5‐(2‐trifluoromethyl‐1,1,1‐trifluoro‐2‐hydroxylpropyl)‐2‐norbornene. The vinyl ether monomers were ethyl vinyl ether, t‐butyl vinyl ether, and 3,4‐dihydro‐2‐H‐pyran. Vinylene carbonate was found to copolymerize with TBTFMA. Although none of the monomers underwent radical homopolymerization under normal conditions, they copolymerized readily, producing a copolymer containing 60–70 mol % TFMA. The copolymerization of the TFMA monomer with norbornenes and vinyl ethers deviated from the terminal model and could be described by the penultimate model. The copolymers of TFMA reported in this article were evaluated as chemical amplification resist polymers for the emerging field of 157‐nm lithography. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1478–1505, 2004     

Mechanism of catalytic asymmetric hydrogenation of 2-formyl-1-methylene-1,2,3,4-tetrahydroisoquinoline using Ru(CH3COO)2[(S)-binap]

The mechanism of the asymmetric hydrogenation of 2-acyl-1-alkylidene-1,2,3,4-tetrahydroisoquinolines, the first reported reaction with the Noyori-Takaya Ru(CH₃COO)₂(binap) complex, has been investigated by means of deuterium labeling, kinetics, and NMR analysis. A series of experiments has revealed that (1) a monohydride-unsaturated mechanism operates involving the initial formation of RuH followed by reaction with the enamide substrate, (2) the hydride transfer from RuH to the olefinic double bond is endothermic and reversible, and (3) the rate is determined in the hydrogenolysis step. This view is consistent with that of proposed for the BINAP-Ru catalyzed Kagan reaction.     

Polybenzimidazoles containing anthracene photodimer

Polybenzimidazoles that contained anthracene photodimer were prepared. The molecular weights of the polymers prepared by the photopolymerization of bis-anthrylbenzimidazoles were limited by the precipitation of the resulting polymers from the reaction organic solvents. Higher molecular weight polymers were obtained by the photopolymerization of bis-anthryl-Schiff's bases, followed by the oxidation of the resulting polymers. These polymers were soluble in acidic solvents such as formic and sulfuric acids but were insoluble in organic solvents.     

Ruijsenaars' Commuting Difference Operators as Commuting Transfer Matrices

For Belavin's elliptic quantum R-matrix, we construct an L-operator as a set of difference operators acting on functions on the type A weight space. According to the fundamental relation RLL=LLR, taking the trace of the L-operator gives a set of commuting difference operators. We show that for the above mentioned L-operator this approach gives Macdonald type operators with elliptic theta function coefficient, actually equivalent to Ruijsenaars' operators. The relationship between the difference L-operator and Krichever's Lax matrix is given, and an explicit formula for elliptic commuting differential operators is derived. We also study the invariant subspace for the system which is spanned by symmetric theta functions on the weight space. Received: 27 December 1995 / Accepted: 11 November 1996     

Mesomorphic properties of orthopalladated complexes of laterally substituted azobenzene derivatives, 2-alkoxycarbonyl-4-(4-ethoxyphenylazo)phenyl 4-methoxybenzoates

Homologous series of 2-alkoxycarbonyl-4-(4-ethoxyphenylazo)phenyl 4-methoxybenzoates (L) and their orthopalladated μ-chloro dimers (Pd₂Cl₂L₂) have been synthesized and their thermotropic phase transition behaviour has been characterized. The ligands, L, are three-ring nematogens with their central rings substituted in the 2-position by n-alkyl chains of varied length. The thermal stability of the nematic phases decreases rapidly with increasing side chain length and then levels off as the series is ascended. In every case the mesomorphic phase appears only over a small temperature range (less than 20° C). The orthopalladated species also proved to be nematogenic. Melting and clearing points rise on the average by 87° C and 126° C, respectively, and thus the temperature ranges of the nematic phases are enlarged considerably upon metallation. In relation to the observed stabilization of the nematic phases, particularly of higher homologues, a lath-like molecular structure, in which the side chains of the ligands fill up the clefts of the core part, has been deduced for a Pd2Cl2L2 homologue from its solution ¹H-NMR spectrum.     

Hetergeneous-nucleation synthesis of monodisperse ε-cobalt nanoparticles using palladium seeds

Monodisperse bimetallic Pd–Co nanoparticles were prepared via a thermal decomposition of cobalt carbonyl using palladium seeds at the Pd/Co molar ratios 0.5%, 1%, and 5%. The heterogeneously nucleated nanoparticles without any size-selective precipitation are sufficiently uniform to self-assemble into ordered arrays. The as-synthesized nanoparticles are each a single crystal with a complex cubic structure called ε-Co. The presence of Pd seeds seems to improve the stability of Co nanoparticles against oxidation based on the results from time-dependent magnetization measurement.     

Existence of solution for Eguchi-Oki-Matsumura equation describing phase separation and order-disorder transition in binary alloys

In this paper we consider the Eguchi-Oki-Matsumura equation which consists of the fourth- and second-order coupled equations of parabolic type. It is shown that this system admits the unique global solution.     

Preparation and condensation reactions of a new light-fluorous Mukaiyama reagent: reliable purification with fluorous solid phase extraction for esters and amides

A modified light-fluorous Mukaiyama reagent bearing a C₈F₁₇ tag was prepared and examined in ester and amide forming condensation reactions. Following the reactions, the desired product was effectively separated from the fluorous pyridone by-product using a simple fluorous solid phase extraction.     

Major-to-ultratrace elements in bone-marrow fluid as determined by ICP-AES and ICP-MS.

The major-to-ultratrace elements in human bone-marrow fluid were determined by ICP-AES (inductively coupled plasma atomic emission spectrometry), and ICP-MS (inductively coupled plasma mass spectrometry). The bone-marrow fluid sample was centrifuged prior to acid digestion to exclude the bone piece from bone marrow, and then digested with nitric acid. As a result, 20 elements could be determined over the concentration range from 1610 microg g(-1) for Na to 0.00043 microg g(-1) for W. It was found that Fe, Zn and Sb were enriched by ca. 264-, 7- and 15-fold, respectively, in bone-marrow fluid, compared to those in human blood serum. Alkali metals (K, Rb, Cs), except for Na, were also significantly enriched in bone-marrow fluid. Furthermore, the concentrations of various elements, such as Fe, P, Al, Zn, Cu, Se, Zr, Sn, Ag and W, were significantly higher than those in open seawater.     

Determination of hexabromocyclododecane diastereoisomers and tetrabromobisphenol A in water and sediment by liquid chromatography/mass spectrometry.

A method to determine alpha-, beta- and gamma-hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) in water and sediments was presented using solid phase extraction (SPE) and/or solvent extraction. Recoveries from sediments were approximately 100% for all the chemicals, while recoveries of alpha-, beta- and gamma-HBCDs from water were dependent on the extraction method. In the case of dichloromethane (CH2Cl2) extraction, recoveries of alpha-, beta- and gamma-HBCD from landfill leachates were 77%, 88% and 92%, respectively. Technical difficulties in HBCD measurement are discussed in terms of the physico-chemical properties of HBCD isomers. The method was applied to landfill samples and marine sediment.