Poly[(R)-3-hydroxybutyric acid] [R-P(3HB)] was hydrolyzed in high-temperature and high-pressure water at the temperature range of 180-300 degrees C and for a period of 360 min. The formation, racemization, and decomposition of 3-hydroxybutyric acids (3HBs) and molecular weight change of R-P(3HB) were investigated. The highest yield of (R)-3-hydroxybutyric acid (R-3HB), ca. 80%, was obtained at 200 degrees C in the hydrolytic degradation periods of 240-360 min. Too-high hydrolytic degradation temperature such as 300 degrees C induced the decomposition and racemization of formed 3HBs, resulting in decreased yield of R-3HB. The hydrolytic degradation of R-P(3HB) proceeds homogeneously and randomly via a bulk erosion mechanism. The molecular weight of R-P(3HB) decreased exponentially without formation of low-molecular weight specific peaks originating from crystalline residues. The hydrolytic degradation rates in the melt estimated from M. changes were lower for R-P(3HB) than for poly(L-lactide) (PLLA) in the temperature range of 180-220 degrees C. The activation energy for the hydrolytic degradation (Delta E-h) of R-P(31413) in the melt (180-250 degrees C) was 30.0 kcal mol(-1), which is higher than 12.2 kcal mol(-1) for PLLA in the melt in the temperature range (180-250 degrees C). This study reveals that hydrolytic degradation of PHB in the melt is an effective and simple method to obtain (R)-3HB and to prepare R-P(3HB) having different molecular weights without containing the specific low-molecular-weight chains, because of the removal of the effect caused by crystalline residues. (c) 2005 Elsevier Ltd. All rights reserved.