Candida antartica lipase B catalyzed polycaprolactone synthesis: effects of organic media and temperature.
Engineering of the reaction medium and study of an expanded range of reaction temperatures were carried out in an effort to positively influence the outcome of Novozyme-435 (immobilized Lipase B from Candida antarctica) catalyzed epsilon-CL polymerizations. A series of solvents including acetonitrile, dioxane, tetrahydrofuran, chloroform, butyl ether, isopropyl ether, isooctane, and toluene (log P from -1.1 to 4.5) were evaluated at 70 degrees C. Statistically (ANOVA), two significant regions were observed. Solvents having log P values from -1.1 to 0.49 showed low propagation rates (< or = 30% epsilon-CL conversion in 4 h) and gave products of short chain length (Mn < or = 5200 g/mol). In contrast, solvents with log P values from 1.9 to 4.5 showed enhanced propagation rates and afforded polymers of higher molecular weight (Mn = 11,500-17,000 g/mol). Toluene, a preferred solvent for this work, was studied at epsilon-CL to toluene (wt/vol) ratios from 1:1 to 10:1. The ratio 1:2 was selected since, for polymerizations at 70 degrees C, 0.3 mL of epsilon-CL and 4 h, gave high monomer conversions and Mn values (approximately 85% and approximately 17,000 g/mol, respectively). Increasing the scale of the reaction from 0.3 to 10 mL of CL resulted in a similar isolated product yield, but the Mn increased from 17,200 to 44,800 g/mol. Toluene appeared to help stabilize Novozyme-435 so that lipase-catalyzed polymerizations could be conducted effectively at 90 degrees C. For example, within only 2 h at 90 degrees C (toluene-d8 to epsilon-CL, 5:1, approximately 1% protein), the % monomer conversion reached approximately 90%. Also, the controlled character of these polymerizations as a function of reaction temperature was evaluated.
Kumar
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NSF Center for Biocatalysis and Bioprocessing of Macromolecules, Polytechnic University, Department of Chemistry and Chemical Engineering, Six Metrotech Center, Brooklyn, New York 11201, USA. Kumar@poly.edu, rgross@poly.edu
Gross
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D002175:Candida / Q000201:enzymology*; D002208:Caproates / Q000737:chemistry; D003470:Culture Media; D007700:Kinetics; D007783:Lactones / Q000737:chemistry; D008049:Lipase / Q000737:chemistry*; D008970:Molecular Weight; D011091:Polyesters / Q000138:chemical synthesis*; D012997:Solvents; D013696:Temperature
D002208:Caproates; D003470:Culture Media; D007783:Lactones; D011091:Polyesters; D012997:Solvents; C016240:polycaprolactone; C121056:caprolactone; D008049:Lipase