No abstract

Polyadditions of 1,2‐bis[3‐(1,3‐dioxan‐2‐one‐5‐yl)‐propylthio]ethane (B6CC) and 1,2‐bis[4‐(1,3‐dioxolan‐2‐one‐4‐yl)‐butylthio]ethane (B5CC) with 4,9‐dioxadodecane‐1,12‐diamine were carried out. The reactivity of B6CC with the diamine was higher than that of B5CC. Additionally, B6CC gave a higher molecular weight polymer than B5CC. The reaction‐rate constants of B6CC and B5CC at 30, 50, and 70 °C were evaluated as 0.70, 0.89, and 1.07 L/mol · h; and 0.03, 0.06, and 0.10 L/mol · h in N,N‐dimethylacetamide (initial reagent concentration 0.5 M), respectively. The activation energies were estimated to be 9.2 and 24.9 kJ/mol in the reactions of B6CC and B5CC with the diamine, respectively. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 860–867, 2001

SYNOPSISBis (cyclic carbonate) s 1 were prepared by the reaction of bis (epoxide) s and atmospheric pressure of COP in the presence of sodium iodide and triphenylphosphine as catalysts at 100°C in high yield. Polyaddition of 1 and hexamethylenediamine ( 2a) or dodecamethylenediamine (2b) in dimethylsulfoxide or N,N-dimethylacetamide ( DMAc) at 70 or 100°C for 24 h afforded corresponding poly ( hydroxyurethane) s with M,, 20,000-30,000. When ethylenediamine (2c) or 1,3-propanediamine (2d) was used as a diamine, poly( hydroxyurethane) s with lower molecular weight were obtained. The presence of water, methanol, or ethyl acetate in the solvent had little effect on the M,, of the polymer obtained, because of the high chemoselectivity of the reaction of the five-membered cyclic carbonate and amine. Polyaddition of bis (cyclic carbonate) bearing ester groups and 2a also afforded the corresponding poly ( hydroxyurethane) without aminolysis of the ester groups. Poly ( hydroxyurethane) 3 obtained from the bis (cyclic carbonate) derived from bisphenol A was less soluble in organic solvents than model polyurethane 8 having no hydroxy groups obtained from 4,4'-isopropylidenebis ( 2-hydroxyethoxybenzene ) and hexamethylene diisocyanate, and was thermally stable as well as 8. 3 easily undertook crosslinking a t room temperature by the treatment with hexamethylene diisocyanate or aluminium triisopropoxide in DMAc or tetrahydrofuran. The gel crosslinked by aluminium triisopropoxide regenerated the original polymer at room temperature by treatment with 1.5 equiv of 1.2M HC1 in N-methylpyrollidinone for 1 h. 0 1993 John Wiley & Sons, Inc.

Various polymeric phosphonium salts and the corresponding low‐molecular‐weight model compounds were prepared and their antibacterial activities against Staphylococcus aureus and Escherichia coli were explored by the viable cell counting method in sterile distilled water. Antibacterial activity of the polymers was found to be higher than that of the corresponding model compounds, particularly against S. aureus. Furthermore, the polymeric phosphonium salt exhibited a higher activity by 2 orders of magnitude than the polymeric quaternary ammonium salt with the same structure except the cationic part. Compounds with the longest alkyl chain (octyl) studied were found to exhibit particularly high activity, and this finding may be ascribed to the contribution of the increased hydrophobicity of the compounds to the cidal activity. © 1993 John Wiley & Sons, Inc.

Anionic equilibrium polymerization behavior of several six-membered cyclic carbonates was examined. The conversions of the monomers reached a constant below 100%, and the final conversion decreased in the order of 1,3-dioxan-2-one (1) > 5,5-dimethyl-1,3-dioxan-2-one (2) > 5,5-diethyl-1,3-dioxan-2-one (3) ≥ 5-methyl-5-phenyl-1,3-dioxan-2-one (4) > 5-ethyl-5-phenyl-1,3-dioxan-2-one (5). The reactions of 2,2-disubstituted-1,3-propanediols were carried out with phosgene dimer to find that the cyclic carbonate (5) was formed quantitatively in the reaction of 2-ethyl-2-phenyl-1,3-propanediol, while the corresponding polycarbonate was formed in the reaction of 2,2-diethyl-1,3-propanediol in 24% yield besides 3. Thermodynamic parameters were estimated in the anionic ring-opening polymerizations of cyclic carbonates (1−5) by Dainton's equation. The obtained ΔH p value in the ring-opening polymerization of each cyclic carbonate reflected the polymerizability. Molecular orbital calculations of the model compounds of the polymers were carried out to find that the polymerizabilities of the cyclic carbonates correlated with the stabilities of the corresponding polymer structures. The concentrations of the monomers formed in the depolymerizations well agreed with the equilibrium monomer concentrations in the anionic ring-opening polymerizations.