Preparation of polymethyl methacrylate with well-controlled stereoregularity by anionic polymerization in an ionic liquid solvent

This study investigates the effect of ionic liquids (ILs) on the anionic polymerization of methyl methacrylate (MMA). Polymethyl methacrylate (PMMA), an isotactic polymer, is prepared by anionic polymerization at a high reaction temperature with an IL that acts as both solvent and additive. The most plausible reaction mechanism is determined using ¹H NMR and Fourier-transform infrared spectroscopy. The electrostatic interaction between MMA and the IL increases the apparent steric hindrance in MMA, resulting in the isotactic PMMA.     

Control of the size and characteristic features of fluorine-containing aromatic polyamide particles

Nano-sized aromatic polyamide particles with trifluoromethyl groups were prepared via a precipitation polymerization method from 4,4′-diphenyldicarbonyl chloride and 2,2-bis(4-aminophenyl)hexafluoropropane in a dioxane solution containing pyridine. The average diameter of the particles decreased from ca. 500 to 150 nm as the pyridine content increased. The particles were spherical with narrow size distributions. Also, the inherent viscosity and yield of the particles decreased gradually as the pyridine content increased. For all the particles, the degrees of crystallinity were low, and the thermal decomposition temperatures were above 457 °C. The addition of pyridine significantly influenced not only the polymerization but also the affinity between the product and the reaction solution, resulting in a difference in the diameters and characteristic features of the particles. Furthermore, these characteristic features were found to be determined predominantly during precipitation from the reaction solution. Meanwhile, trifluoromethyl groups in the particles had significant influence on the morphology and characteristic features of the particles.     

Extremal solutions for stochastic equations indexed by negative integers and taking values in compact groups

Stochastic equations indexed by negative integers and taking values in compact groups are studied. Extremal solutions of the equations are characterized in terms of infinite products of independent random variables. This result is applied to characterize several properties of the set of all solutions in terms of the law of the driving noise.     

Synthesis and Magnetic Property of Polyacetylene Bearing πConjugated Bis(Diphenylene)Phenylallyl Radical

Abstract

m- and p Bis(diphenylene)propenylphenylacetylene (m-, p-8) were synthesized and polymerized with WCI₆, MoCl₅, and Rh catalyst, yielding solvent-soluble poly(phenylacetylene)s bearing a π-conjugated bis(di-phenylene)propenyl groups (m-, p-7a). The polymers gave their polyanion derivatives, which were electrolytically and chemically oxidized to yield the corresponding polyradicals (m-, p-7b). The polyradicals were chemically very stable due to the resonance stabilization of an unpaired electron whose spin concentration could be increased up to ca. 2 × 10²³ spins per molar monomer unit. ESR spectroscopy suggested an antiferro-magnetic interaction between unpaired electrons.     

Complexation Constants of Lanthanide Ions with Poly(Methacrylic Acid) and its Copolymers

Complexation of some lanthanide ions with poly(methacrylic acid) and its copolymers was studied by potentiometric titration. Poly [methacrylic acid-co-oligo(ethylene oxide)methacrylate] and poly(methacrylic acid-co-acrylamide) formed tris-carboxylate coordinate lanthanide complexes with large overall complexation constants, while poly-(methacrylic acid)s and copolymer with higher content of the methacrylic acid residue formed bis-coordinate ones. It was concluded that the comonomer residues in the copolymer chains decreased the steric hindrance for the complexation and/or acted as co-coordinating groups of the carboxylic group to lanthanide ions. Very large positive and favorable entropy changes were observed for the complexation with poly(methacrylic acid) and its copolymers. This contribution of thermodynamic parameters to the complexation was contrary to that for the analogous monomeric methacrylic acid complex and is assumed to be induced by dehydration of the polymers through the lanthanide ion complexation.