Copolymerization of vinylsilanes with styrene

New vinylsilanes (M₂), i. e. phenylvinylsilane (I), allylmethylsilane (II), allylphenylsilane (III), and p-vinylphenylmethylsilane (IV), were prepared and copolymerized with styrene (M₁). The monomer reactivity ratios were r₁ = 5.7 and r₂ = 0, r₁ = 36 and r₂ = 0, r₁ = 29 and r₂ = 0₁, and r₁ = 0.91 and r₂ = 1.1, respectively. From the results of infrared and NMR spectra it was indicated that the vinylsilanes participated in copolymerization in the form of a vinyl type of polymerization and not in the form of a hydrogen-transfer type of polymerization. The reaction of copolymer with alcohols and methyl methacrylate and appropriate catalysts was investigated.     

Insulating tubular BN sheathing on semiconducting nanowires

An effective method was developed for generation of insulating tubular boron nitride (BN)-sheathed nanostructures. ZnS nanowires and multilayered Si-SiO2 nanowires were successfully sheathed with insulating tubular BN-forming nanocables. Both the semiconductor nanowire cores and the BN sheaths are crystalline with well-uniform morphologies.     

A mesoporous non-precious metal boride system: synthesis of mesoporous cobalt boride by strictly controlled chemical reduction

Generating high surface area mesoporous transition metal boride is interesting because the incorporation of boron atoms generates lattice distortions that lead to the formation of amorphous metal boride with unique properties in catalysis. Here we report the first synthesis of mesoporous cobalt boron amorphous alloy colloidal particles using a soft template-directed assembly approach. Dual reducing agents are used to precisely control the chemical reduction process of mesoporous cobalt boron nanospheres. The Earth-abundance of cobalt boride combined with the high surface area and mesoporous nanoarchitecture enables solar-energy efficient photothermal conversion of CO₂ into CO compared to non-porous cobalt boron alloys and commercial cobalt catalysts.

Generating high surface area mesoporous transition metal boride is challenging but interesting because incorporation of boron atoms can generate lattice distortion to form amorphous metal boride which has unique properties in catalysis.     

Studies on the syntheses of heterocylic compounds—762: Synthesis of 3-benzyl-6-methyl-2-oxo-3,6-diazabicyclo[3.1.0]hexane as a synthetic intermediate of mitomycins

(±)-1-Benzyl-3α-hydroxy-4β-methylamino-2-oxopyrrolidine (15) and its cis-isomer (16) were synthesised from 1-benzyl-4-ethoxycarbonyl-2,3-dioxopyrrolidine (2) in several steps. The former (15) was converted to 3-benzyl-6-methyl-2-oxo-3,6-diazabicyclo[3.1.0]hexane (17) with a mixture of triphenylphosphine, carbon tetrachloride and triethylamine.     

Spectroscopic investigation of cyclodextrin monomers,derivatives, polymers and azo dyes (1)

Circular dichroism (CD) and visible spectra of inclusion compounds between Methyl Orange (MO) analogues and -, -, -cyclodextrin (cdx), 2,6-dimethyl-and 2,3,6-trimethyl--cdx, water soluble -, -, -cdx polymer products were investigated. In the CD-spectroscopic investigation, the complex with -cdx epichlorohydrin condensate showed a large amplitude and splitting of the induced ^* band. Fractions of glyceryl ether of less than 2000 and polymer of more than 10000 dalton molecular mass were separated. Complexes of above two fractions and MO showed the same splitting spectral pattern. Job's plots from visible spectra showed the formation of the 11 complex and CD-data suggested the co-existence of the 21 MO-cdx complex. This splitting pattern showed the reversal of the signs when -cdx-ethyleneglycol-bis(epoxypropyl) ether was used and disappeared when larger host molecules and azo dyes were used. The splitting was explained by exciton interaction.     

Synthesis of polyarylamines by vinylogous nucleophilic substitution polymerization of bis(4-chloro-3-nitrophenyl) sulfone with diamines

A series of new polyarylamines was prepared by the vinylogous nuclephilic substitution polymerization of bis(4-chloro-3-nitrophenyl) sulfone with both aromatic and aliphatic diamines. The synthesis involves the solution polycondensation in a polar aprotic solvent at elevated temperatures, a tertiary amine being used as an acid acceptor. Of these solvents, dimethyl sulfoxide and N-methyl-2-pyrrolidone were the most effective for the preparation of high molecular weight polymers. The polyarylamines having inherent viscosities in the range of 0.1–0.5 were all amorphous and highly soluble in polar aprotic solvents. Thermogravimetric analysis under both air and nitrogen atmospheres indicated that rapid decomposition began above 300°C for the polyarylamines from aromatic diamines.     

A facile synthesis of aliphatic polybenzoxazoles from a bis(o-aminophenol) or its hydrochloride and aliphatic dinitriles

A facile one-step method for the synthesis of aliphatic polybenzoxazoles has been developed. Thus, a series of aliphatic polybenzoxazoles having inherent viscosities of 0.2–0.7 dL/g in concentrated sulfuric acid were successfully synthesized by the melt polycondensation of alipatic dinitriles with 4,4′-diamino-3,3′-dihydroxybiphenyl (AHB) or its hydrochloride (AHB–HCl) with the elimination of ammonia or ammonium chloride, respectively. Monomer AHB–HCl was more reactive than the parent AHB, thereby affording higher molecular weight polybenzoxazoles in a shorter reaction time. The aliphatic polybenzoxazoles having 6–10 methylene units were highly crystalline with melting temperatures in the range of 187–308°C, which were stable up to 400°C in a melt state in nitrogen. © 1994 John Wiley & Sons, Inc.