Photopolymerization of cyclohexene oxide by use of o-nitrobenzyl triphenylsilyl ether/aluminum compound catalyst. Dependence of catalyst activity on the structure of the silyl ether

o-Nitrobenzyl triphenylsilyl ehther/aluminum compound has been previously shown by the authors to act as catalyst in the photopolymerization of epoxides. The dependence of the structure of the silyl ether on the catalyst activity was examined. There were two steps in the photopolymerization. The first step (“Step 1”) is photodecomposition of the silyl ether to silanol. The second step (“Step 2”) is the initiation of polymerization by silanol and the aluminum compound. The introduction of an electron withdrawing group, Cl, CF₃, on the benzene ring bonded to Si made the quantum yield of Step 1 low, however, the rate of Step 2 was increased. The low quantum yield of Step 1 was explained in terms of the rate of electron transfer that is controlled by the relative electron density between the CH₂ and NO₂ in the o-nitrobenzyl group. The acceleration of Step 2 was explained in terms of an increase in silanol acidity that was promoted by the introduction of an electron withdrawing group. The overall rate of the photopolymerizatiol depends to a greater degree on the rate of Step 2 than on that of Step 1.     

Fluorinated monomer–styrene copolymer latex particles: I. kinetic studies in a soap-free aqueous medium

Soap-free emulsion copolymerization of 2, 2, 2-trifluoroethyl acrylate (3FEA) with styrene was carried out by using potassium persulfate as an initiator, and the effects of the weight fraction of 3FEA in the monomer feed on the kinetics and the particle size were investigated. Monomer conversions were followed by a gravimetric method, revealing that the overall polymerization rate increased exponentially with an increase in the weight fraction of 3FEA. According to dynamic light scattering measurement, the final particle size was found to decrease with an increase in the weight fraction of 3FEA. The number of particles for 3FEA homopolymerization was roughly twice as large as that at the fraction of 0.9, although both fractions had the almost same polymerization rates. These results indicate that soap-free emulsion homopolymerization of 3FEA would proceed not only inside the polymer particles but also in the aqueous phase throughout the polymerization.     

Dielectric relaxation in the paracrystalline phase in polyacrylonitrile

Thermal expansion and dielectric relaxation of polyacrylonitrile were measured in the temperature range from ?75 to 152°C. at frequencies from 30 cps to 3 Mc./sec. The thermal expansion curve and the temperature dependence of logarithmic relaxation time both show an inflection at 85°C. An x-ray study by Bohn reveals that this inflection comes from the thermal expansion of the paracrystalline phase of this polymer, and consequently the transition at 85°C. and the associated relaxation are ascribed to molecular motion in the paracrystalline phase. The relaxation strength increases with increasing temperature above this point. The transition is caused by freezing of the bending vibration of chains whereas the relaxation results from rotational vibration. The length of segments in this phase is roughly estimated to be ca. 100 A. by comparing the observed relaxation strength with the theory developed on the basis of the above considerations.     

Synthesis of 2-alkylidenetetrahydrofurans by Ru-catalyzed regio- and stereoselective codimerization of dihydrofurans with alpha,beta-unsaturated esters

2-(1-Alkoxycarbonyl)alkylidenetetrahydrofurans were readily synthesized by the codimerization of 2,3- or 2,5-dihydrofurans with alpha,beta-unsaturated esters using a zerovalent Ru catalyst, Ru(cod)(cot), with high regio- and stereoselectivity.     

Localization of Iα and Iβ phases in algal cellulose revealed by acid treatments

Highly crystalline I-rich type Cladophora cellulose, which had been kept in never-dried condition, was treated in 60wt% sulfuric acid at 100°C, for 1–48h. The cellulose microcrystals thus obtained were analysed by X-ray diffractometry, FT-IR, and transmission electron microscopy. The I component was found to be more degraded than the I component. The cellulose I/I ratios of the samples acid-treated for 0, 24, and 48 h were about 8:2, 6:4, and 4:6, respectively. After the acid treatment, the microcrystals became narrower in width, and very sharp at their ends. These results indicate that the I phase is mostly located at the surface of the microcrystals, which is morphologically more susceptible to the acid treatment.     

Radiation-induced heterogeneous polymerization of acrylamide in acetone and acetone–water mixtures

The effects of temperature, dose rate, and monomer concentration on the heterogeneous polymerization of acrylamide in acetone–water mixtures have been studied. Heterogeneous polymerization takes place in mixtures containing less than 60 vol-% water. The polymerization is steady in acetone and nonsteady in acetone an nonsteady in mixtures containing 10–50 vol-% water. The average rate of polymerization is highest in mixtures with about 20 vol-% water. Polymer molecular weight increases with the increasing water content in range 0–10 vol-% and does not change in the range of 30–70 vol-% water. For the polymerization in acetone and an acetone–water 60/40 mixture the activation energies are 2.3 and ?1.8 kcal/mole, the dose rate exponents of rate are 0.78 and 0.52, and the monomer concentration exponents of rate are 0.5 and 1.6, respectively. The polymer molecular weight increases with decreasing dose rate, decreasing temperature, and increasing monomer concentration. These results are discussed in connection with the mechanism of heterogeneous polymerization and the solvent effect.     

Studies on separation mechanisms of biological molecules on a polyvinyl alcohol column

Summary The chromatographic separation mechanism on a polyvinyl alcohol (PVA) column in aqueous systems was explored utilizing several different types of compound such as polyethylene glycols, carbohydrates, pyrimidine and purine bases, fatty acids, monophosphate nucleotides and glycyl-peptides. Two types of separation mechanisms were found to occur for these substrates. The polyethylene glycols and the carbohydrates were eluted by size-exclusion chromatography. The retention behavior of the other substrates could be explained by the solvophobic theory, suggesting that the predominant separation mode was reversed-phase chromatography. The occurrence of reversed-phase chromatography was also indicated by the remarkable effect of the addition of ion-association reagents to the chromatographic system on the retention of the monophosphate nucleotides.     

Effect of phenyl substituent on the dimerization of copper(II)-carboxylate in solvent extraction of copper(II) with phenylacetic acid

The effects of the phenyl substituent on the dimerization of copper(II) carboxylate in the solvent extraction of copper(II) with phenylacetic acid using benzene and 1-octanol as a solvent were investigated, at 25 degrees and at the aqueous ionic strength of 0.1M (NaClO(4)). The dimerization of copper(II) phenylacetate has been found to be written as: 2CuA(2)Cu(2)A(4) in 1-octanol, and 2CuA(2)(HA)(2)Cu(2)A(4)(HA)(2) + (HA)(2) in benzene, with the dimerization constants, log K = 2.24 and log K = 4.19, respectively. It was proved that the phenyl group inhibits the formation of the dimeric copper(II) phenylacetate, and its effect is partially shielded by a methylene substituent.