Cellulose Ester-graft-poly(ε-caprolactone): Effects of Copolymer Composition and Intercomponent Miscibility on the Enzymatic Hydrolysis Behavior

Enzymatic hydrolysis was conducted with Pseudomonas lipase for film samples of graft copolymers of cellulose acetate (CA) and butyrate (CB) with poly(epsilon-caprolactone) (PCL), CA-g-PCL, and CB-g-PCL, respectively. The two trunk polymers CA and CB, both having the degree of acyl substitution (DS) of > 2, are respectively immiscible and miscible with PCL. A hindrance effect of the cellulose ester trunks on the enzymatic attack to the PCL component was observed for the two copolymer series; the situation was more conspicuous in the use of CB trunks. After the selective hydrolytic degradation of the PCL component, a topographical study by AFM revealed that the CA and CB constituents as residues formed a protuberant structure on the surface of the respective film specimens. The altitude and regularity of the protuberances were variant depending on the initial copolymer composition. In a phase-imaging mode of AFM, a hydrolyzed film of CA-g-PCL with an extremely low graft-density (acetyl DS > 2.95) showed particularly larger CA domains of >25 nm in diameter. The domain sizes were in accordance with a heterogeneity scale in the original intercomponent mixing state estimated by H-1 spin-lattice relaxation time (T-1(H)) measurements in solid-state C-13 NMR spectroscopy. The present results demonstrate a high potential in application of the PCL-grafted cellulosic copolymers as spatiotemporally biodegradation-controllable materials.