Laser-ionization mass-spectrometric studies on laser ablation of a nitrogen-rich polymer at 532 nm and 1064 nm

Laser-ionization Time-Of-Flight (TOF) mass-spectrometric studies have been carried out on the 532 nm and 1064 nm laser ablation products from a nitrogen-rich polymer. The polymer used had an elemental composition of C_6.0N_8.9H_3.4 and consisted of C=N, C-N, and N-H chemical bonds. The TOF mass spectra observed were composed of various peaks (150 amu) depending on the ablation laser wavelength. The primary peaks were assigned to C⁺, CN⁺, CHnN⁺ ₂ (n=1–3) and C₂H₂N⁺ ₃ for 532 nm ablation, and C⁺, C⁺ ₃, HCN⁺, HCCN⁺, CH₂NH⁺, HNCN⁺, H₃NCN⁺, and C₄H₄N⁺ ₇ for 1064 nm ablation. The flight velocity distributions with peak velocities ranging from 8.6×10³ cm/s to 3.8×10⁴ cm/s were measured for these products. The distinct velocity distributions observed between small and large products indicate the presence of two origins in the fragment ejection process from the polymer for both 532 nm and 1064 nm ablation. Furthermore, we suggest an importance of the translational energy of the fragments for the product generation in the laser plume.     

Effects of solvent in photo-induced graft copolymerization of vinyl monomers on cellulose

The effects of swelling of the sample and polymerization solvents were studied for photo-induced graft copolymerization of vinyl monomers on cellulose. The graft copolymerization of methyl methacrylate (MMA) was activated by swelling of the sample or organic solvent-water solutions within a certain range of their concentrations. Though each organic solvent gave a maximum in per cent grafting and the number of grafts at about 25 vol-% concentration, the initiation reaction scarcely took place at 100% concentration; thus, the solvent itself is considered to have a negative effect. The solvents used in the experiments were all hydrophilic, such as methanol, acetone, and dioxane. The average molecular weight of the grafted PMMA differed in each solvent, indicating a different characteristic effect of solvent on the growing grafted polymer radicals. The presence of ferric ion as a sensitizer stimulated further the contributions of the sample swelling and the organic solvents to the copolymerization reaction. A similar effect was observed for styrene as for MMA, but not for acrylic acid and methacrylic acid.     

Aromatic polyesters obtained directly from hydroxybenzoic acids by hexachlorocyclotriphosphatriazene (PNC) in pyridine

Polyaryl esters of moderate molecular weights were prepared by the direct polycondensation reaction of hydroxybenzoic acids and its derivatives with hexachlorocyclotriphosphatriazene (also known as phosphonitrilic chloride trimer, PNC) as a condensing agent in pyridine. Copolymerization of p-hydroxybenzoic acid with several hydroxybenzic acid derivatives was carried out to improve the processability of the polymer of p-hydroxybenzoic acid, which yields fusible and soluble copolymers of high inherent viscosities. Polymer solubility and thermal behavior were examined.