Opening and Addition Modes in Propagation During Radical Polymerization of Fumaric and Maleic Derivatives

Abstract

Polymers of bis(trimethylsilyl) fumarate, di-tert-amyl fumarate, and methyl tert-amyl fumarate were prepared by radical polymerization at 60 or 120°C. The polymers were converted into poly(dimethyl fumarate) via thermolysis or hydrolysis and subsequent methylation to determine the tacticity using ¹³C-NMR spectroscopy. The probabilities of meso addition (P _m) were revealed to be 0.66 (60°C) for the bis(trimethylsilyl) ester, 0.60 (60°C) and 0.52 (120°C) for the di-tert-amyl ester, and 0.54 (60 and 120°C) for the methyl tert-amyl ester. From the temperature dependence of the P _m values, the differences in activation enthalpies and entropies for the meso and racemo additions were evaluated. The microstructure of poly(dimethyl fumarate) derived from poly(maleic anhydride) was also examined. The opening and addition modes in propagation of the fumaric and maleic derivatives were discussed based on the results obtained in the present and previous work.     

Facile Synthesis of Oxamides by Efficient Trapping of Carbamoyl Lithiums with Isocyanates

Unsymmetrical oxamides are conveniently synthesized in good yields by a new trapping reaction of unstable carbamoyl lithiums with isocyanates.     

Detailed mechanism of radical high polymerization of sterically hindered dialkyl fumarates

The radical polymerization kinetics and mechanism of sterically hindered dialkyl fumarates (DRF) bearing various ester alkyl groups are described comprehensively. The overall polymerization reactivity of DRF, the initiation mechanism and the reactivity of the primary radicals in the polymerizations with azo initiators, the determination of the propagation and termination rate constants by means of electron spin resonance spectroscopy, the propagation mechanism and the microstructure of the polymers, and the chain rigidity of poly(DRF) and bimolecular termination process are discussed.     

A New Imaging Method with a Spatial Filter for Incoherent Stream

A new imaging method using an incoherent-type pupil filter: SFINCS (Spatial Filter for INCoherent Stream) is presented. The new filter divides the imaging beam into several incoherent beams at the pupil plane thereby enlarging the depth-of-focus (DOF). The capabilities of SFINCS are studied by simulations and several ways to realize the method are also discussed. The experimental results show that SFINCS has excellent DOF expanding capabilities for a point-image such as a hole pattern in VLSI lithography, and that 1.7 μm DOF is obtained with a 0.30 μm hole pattern by an i-line projection lens with 0.57 NA (numerical aperture).Presented at the International Commission for Optics Topical Meeting, Kyoto, 1994.     

M1 gamma strength for zirconium nuclei in the photoneutron channel

Photoneutron cross sections were measured for 91Zr, 92Zr, and 94Zr near the neutron separation energy with quasimonochromatic gamma rays. The data exhibit some extra components around the neutron threshold. A coherent analysis of the photoneutron data for 92Zr together with the neutron capture on 91Zr based on the microscopic Hartree-Fock-Bogoliubov plus quasiparticle random-phase approximation model for the E1 strength has revealed the presence of an M1 resonance at 9 MeV. The microscopic approach systematically shows the same M1 strength in the photoneutron cross section for 91Zr and 94Zr. The total M1 strength is about 75% larger than the strength predicted by the systematics, being qualitatively consistent with the giant M1 resonance observed in the inelastic proton scattering.