Click chemistry in materials synthesis. III. Metal‐adhesive polymers from Cu(I)‐catalyzed azide–alkyne cycloaddition

1,2,3‐Triazole‐based polymers generated from the Cu(I)‐catalyzed cycloaddition between multivalent azides and acetylenes are effective adhesive materials for metal surfaces. The adhesive capacities of candidate mixtures of azide and alkyne components were measured by a modified peel test, using a customized adhesive tester. A particularly effective tetravalent alkyne and trivalent azide combination was identified, giving exceptional strength that matches or exceeds the best commercial formulations. The addition of Cu catalyst was found to be important for the synthesis of stronger adhesive polymers when cured at room temperature. Heating also accelerated curing rates, but the maximum adhesive strengths achieved at both room temperature and high temperature were the same, suggesting that crosslinking reaches the same advanced point in all cases. Polytriazoles also form adhesives to aluminum, but copper is bound more effectively, presumably because active Cu(I) ions may be leached from the surface to promote crosslinking and adhesion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5182–5189, 2007     

Phonon scattering from the boundaries of small crystals embedded in a dielectric porous-glass matrix

The thermal conductivity of porous glass with randomly distributed connecting pores ～70 Å in size (glass porosity ～25%), as well as of a porous glass + NaCl composite, was measured in the temperature range 5–300 K. NaCl filled one fourth of the pores in the composite. The experimental results on the composite thermal conductivity can be accounted for only by assuming that phonons scatter from the boundaries of NaCl nanocrystals embedded in channels of the porous glass.     

Reaction of chlorine fluosulfate with fluorinated alcohols and some properties of polyfluoroalkyl hypochlorites

Conclusions Stable ,-dihydropolyfluoroalkyl hypochlorites were obtained by reacting ClOSO₂F with fluorinated alcohols, and some of their chemical properties were studied.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2369–2374, October, 1980.     

Reaction of nitronium fluosulfate with fluoroolefins

Conclusions We were the first to add nitronium fluosulfate to the multiple bond of fluoroolefins to give the corresponding fluorinated -nitroalkyl fluosulfates. The theory was expressed that the electrophilic mechanism applies to the given process.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1437–1441, June, 1983.     

The protonation of gaseous cyclopropane

The protonation of cyclopropane by gaseous Br?nsted acids of varying strength in radiolytic experiments at atmospheric pressure leads to two distinct C3H7- isomers that have been sampled by their reaction with benzene. The neutral end products, nC3H7-C6H5 and iC3H7-C6H5, arise from the electrophilic aromatic substitution reaction with the cC3H7+ and iC3H7+ ions, respectively. Their relative abundance was studied as a function of pressure, temperature, and the presence of additives in the gaseous systems; the results indicate a large extent of isomerization to the thermodynamically favored iC3H7+ from the protonation by strong acids. The presence of a kinetic barrier prevents any thermal isomerization from taking place in the time frame of 10(-8) s. In the peculiar case in which protonated benzene is the Br?nsted acid, C3H7+ ions are formed in the presence of neutral benzene within the same ion - molecule complex. The ensuing reaction shows that cC3H7+ ions are formed exclusively and react in the 10(-10) s(-1) estimated lifetime of the complex. Still, such cC3H7+ ions undergo complete randomization of their hydrogen atoms; this points to a low kinetic barrier for the process. Agreement is found between the reported experimental results and updated computations of the relevant species in the C3H7+ potential energy surface.     

Formation of 2,2-difluoro-3-hydroxymethylbenzo-1,4-oxathianes from 2-(α-trifluoromethylvinylthio)phenols)

It is shown that 2,2-difluoro-3-hydroxymethylbenzo-1,4-oxathianes are formed together with 3-trifluoromethylbenzo-1,4-oxathianes whenortho-(-trifluoromethyl--chloroethylthio)phenols are boiled with excess aqueous alkali. The mechanism of the reaction is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1457–1459, August, 1994.