A Reductive homo-coupling polymerization of aromatic diisocyanates promoted by samarium iodide

The selective reductive homo-coupling polymerization of aromatic diisocyanates via one-electron transfer promoted by samarium iodide in the presence of hexamethylphosphoramide (HMPA) produced the corresponding poly(oxamide)s ( 1 ) nearly quantitatively. The ob-tained polymers were insoluble in common organic solvents. The alkylation of 1 with methyl iodide or allyl bromide in the presence of potassium tert-butoxide provided the highly soluble alkylated polymer in good yields. In either case, the alkylation was almost complete, and both N-and O-alkylation proceeded. The ratio of N-and O-methylation was found to be 64 : 36 by ¹H-NMR spectrum, and that of N- and O-allylation was 3 : 1 from ¹³C-NMR analysis. The present polymerization system could be applied to a variety of diisocyanates, including diphenylmethanediisocyanate (MDI), tolylene 2,6-diisocyanate (TDI), 2,6-naphthyl diisocyanate (NDI) and o-tolidine diisocyanate (TODI). The molecular weights of the polymers were estimated by GPC and found to be 2000–9000. The TGA measurement of the corresponding polymers showed T_d10 at 248–320°C. © 1995 John Wiley & Sons, Inc.     

Synthesis and radical ring-opening polymerization of spiro o-carbonates

Syntheses and radical ring-opening polymerization of spiro o-carbonates(I-IV) were investigated. These polymers were yellow powders and soluble in common organic solvents. The infrared and NMR spectra indicated that the polymers were alternate copolymers of either and carbonate containing double bonds. The polymerization mechanism is discussed.     

Monomer-isomerization polymerization. XXVI. Formation of polyallylcyclohexane from propenylcyclohexane through monomer-isomerization polymerization with Ziegler–Natta catalysts

Monomer-isomerization polymerization of propenycyclohexane (PCH) with TiCl₃ and R_3-xAICI_x (R = C₂H₅ or i-C₄H₉, x = 1–3) catalysts was studied. It was found that PCH underwent monomer-isomerization polymerization to give a high molecular weight polymer consisting of an allylcyclohexane (ACH) repeat unit. Among the alkyaluminum cocatalysts examined, (C₂H₅)₃Al was the most effective cocatalyst for the monomer-isomerization polymerization of PCH, and a maximum for the polymerization was observed at a molar ratio of Al/Ti of about 2.0. The addition of isomerization catalysts such as nickel acetylacetonate [Ni(acac)₂] to the TiCl₃–(C₂H₅)₃Al catalyst accelerated the monomer-isomerization polymerization of PCH and gave a maximum for the polymerization at a Ni/Ti molar ratio of 0.5. PCH also undergoes monomer-isomerization copolymerization with 2-butene (2B).     

A study of the reactions π+p→ K+∑+ and K−p→π−∑+ at 10 GeV/c

For the first time, the reactions π⁺p→K⁺∑⁺ and K^?p→π^?∑⁺ have been studied in the same apparatus. This has been done at an adequately high momentum (10.1 GeV/c) to allow a check of the prediction of exchange degeneracy, that the differential cross sections should be converging at high energy. We have measured the cross section for momentum transfers t between t_min and t = ?0.3 (GeV/c)². We find that for both reactions the differential cross section shows an exponential fall, with no deviations right in to t =t_min (where some other experiments have shown a dip in the cross section). Furthermore, we find the magnitude of the differential cross sections to be closely similar at t = 0, with a ratio

$\text{R=}\text{(}\text{d}\text{σ}\text{d}\text{t)}{}_{\mathrm{t=0}}\text{(}\text{K}{}^{\mathrm{?}}\text{p}\text{→π}{}^{\mathrm{?}}\text{∑}{}^{\mathrm{+}}\text{)}\text{(}\text{d}\text{σ}\text{d}\text{t)}{}_{\mathrm{t=0}}\text{(π}{}^{\mathrm{+}}\text{p}\text{→}\text{K}{}^{\mathrm{+}}\text{∑}{}^{\mathrm{+}}$

However, the slope for the positive reaction is about 19% steeper than that for the negative reaction.     

Calibration of the isomer shift of125Te from internal conversion and mössbauer measurement

Radioactive¹²⁵I was ion-implanted into 7 different metal matrices. Al, Au, In, Pt, Sn, Te and Zn, and internal conversion and Mössbauer spectra associated with the 35.46 keV M1 transition of¹²⁵Te were measured for the same samples. A value R/R=(0.853±0.115)×10^–4 was derived for the relative difference of the nuclear charge radius for the 35.46 keV M1 transition of¹²⁵Te.     

Enthalpic changes on mixing two couples of S- and R-enantiomers of heptane-2-ol, octane-2-ol, nonane-2-ol, 3-chloro-propane-1,2-diol, 2-methyl-1,4-butanediol at 298.15 K

Enthalpies of mixing of (R)- and (S)-enantiomers of liquid chiral compounds such as heptane-2-ol, octane-2-ol, nonane-2-ol, 3-chloro-propane-1,2-diol and 2-methyl-1,4-butanediol have been measured over a range of mole fractions at 298.15 K, albeit very small values. Mixing of heterochiral liquids of heptane-2-ol, octane-2-ol, nonane-2-ol, 3-chloro-propane-1,2-diol, realized enthalpic destabilization over the whole range of mole fractions, whereas that of 2-methyl-1,4-butanediol realized enthalpic stabilization over entire compositions. The maximum values of enthalpies of mixing and the intermolecular interaction of cohesive energy density and entropy of vaporization showed a linear correlation except for the compounds having two chiral centers and others.     

Assembly of an Axially Chiral Dynamic Redox System with a Perfluorobiphenyl Skeleton into Dumbbell‐ or Tripod‐type Electron Donors

The incorporation of F atoms endows a diethenylbiphenyl‐based electron donor with configurational stability and S_NAr reactivity. The former enables the dynamic redox pair of (R_ax)‐ 1 /(R_ax,R,R)‐ 1 ²⁺ to exhibit drastic UV/Vis and CD spectral changes upon electrolysis, whereas the latter makes it possible for (R_ax)‐ 1 to serve as a useful chiral synthon for the production of larger assemblies [(R_ax,R_ax)‐ 2 d,p,m and (R_ax,R_ax,R_ax)‐ 3 ] containing two or three dyrex units. These dyads and triad also exhibit a clean electrochiroptical response with isosbestic points owing to one‐wave multi‐electron transfer.     

Switching non-local vector median filter

This paper describes a novel image filtering method that removes random-valued impulse noise superimposed on a natural color image. In impulse noise removal, it is essential to employ a switching-type filtering method, as used in the well-known switching median filter, to preserve the detail of an original image with good quality. In color image filtering, it is generally preferable to deal with the red (R), green (G), and blue (B) components of each pixel of a color image as elements of a vectorized signal, as in the well-known vector median filter, rather than as component-wise signals to prevent a color shift after filtering. By taking these fundamentals into consideration, we propose a switching-type vector median filter with non-local processing that mainly consists of a noise detector and a noise removal filter. Concretely, we propose a noise detector that proactively detects noise-corrupted pixels by focusing attention on the isolation tendencies of pixels of interest not in an input image but in difference images between RGB components. Furthermore, as the noise removal filter, we propose an extended version of the non-local median filter, we proposed previously for grayscale image processing, named the non-local vector median filter, which is designed for color image processing. The proposed method realizes a superior balance between the preservation of detail and impulse noise removal by proactive noise detection and non-local switching vector median filtering, respectively. The effectiveness and validity of the proposed method are verified in a series of experiments using natural color images.