Takao Yashiro

Hafnium Chloride Catalyzed Polycondensation of α,ω-Alkanediol with Dicarboxylic Acids or Succinic Anhydride

Three different kinds of polycondensation were preformed and the usefulness of HfCl4.2THF as estrification and polycondensation catalyst was evaluated. It was compared with HfCl4, BiCl3, LaCl3 and SnCl2. In polycondensations of 1,6-hexandiol, and 1,10-decandiol with various dicarboxylic acids all catalysts failed to give satisfactory results. However, in polycondensations of 1,4-butanediol with succinic anhydride in refluxing decalin good results were obtained, and HfCl4.2THF was the most effective catalyst after SnCl2. The MALDI-TOF mass spectra revealed that cyclization made a significant contribution to the limitation of the chain growth.

Syntheses of Poly(butylene succinate) by Means of Non-Toxic Catalysts

The usefulness of bismuth, calcium, magnesium and zinc salts for the preparation of poly(butylene succinate), PBSu, was studied. Two different approaches were compared. Firstly, 1,4-butanediol (or in a few experiments ethanediol) dimethyl succinate were condensed at temperatures up to 240°C in the presence of Bi2O3. Regardless of the feed ratio, only low molar mass polyesters having two diol endgroups were obtained. Secondly, 1,4-butanediol and succinic anhydride were polycondensed in refluxing decalin with azeotropic removal of water. BiCL3, BiBr3, BiI3, and Bi-triflate were used as catalyst and the monomer/catalyst ratio was varied. The highest molar masses were achieved with BiCl3. Analogous polycondensations catalysed with ZnCl2, Zn-triflate, MgCl2, Mg-triflate and CaCl2 were unsuccessful. Yet the BiCl3, decalin method was also successfully applied to the combination of succinic anhydride and 1,5-pentanediol.

Polycondensations of Substituted Maleic Anhydrides and 1,6-Hexanediol Catalyzed by Metal Triflates

Polycondensations of methylmaleic anhydride (citraconic anhydride, CiAh), bromomaleic anhydride (BMaAh), and dichloromaleic anhydride (DCMaAh) with 1,6-hexanediol were conducted in bulk. For polycondensations of CiAh, the triflates of aluminum, bismuth, lanthanum, magnesium, samarium, and scandium were used as catalysts and the best results were obtained with Bismuth triflate. MALDI-TOF mass spectra indicated that the chain growth was limited by cyclization and incomplete conversion, but temperatures above 100°C were not advantageous due to side reactions. Bismuth and samarium triflate catalyzed polycondfensations of BMaAh and DCMaAh were less successful than polycondensations of CiAh. For polycondensations of CiAh, BMaAh, and DCMaAh, only a low extent of isomerization to trans isomers (1–3%) was observed at 100°C, but considerably higher extent at 140°C.