Synthesis of Lactide from Oligomeric PLA: Effects of Temperature, Pressure, and Catalyst

Dong Keun Yoo; Dukjoon Kim; Doo Sung Lee

Macromolecular Research, Vol.14, No.5, 510-516, October, 2006

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Synthesis of Lactide from Oligomeric PLA: Effects of Temperature, Pressure, and Catalyst

Dong Keun Yoo, Dukjoon Kim^†, and Doo Sung Lee¹

Department of Chemical Engineering, Polymer Technology Institute, Sungkyunkwan University, Suwon, Gyeonggi 440-746, Korea
¹Department of Polymer Engineering, Polymer Technology Institute, Sungkyunkwan University, Suwon, Gyeonggi 440-746, Korea

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Lactide was produced from oligomeric PLA by back-biting reaction of the OH end groups. For optimization of the reaction conditions, the effects of temperature, pressure, PLA molecular weight, and catalyst type on the lactide synthesis were examined. The fraction of D,L-lactide decreased with increasing temperature. Among the various Sn-based catalysts, the D,L-lactide fraction was maximized when SnO was used. A higher yield with lower racemization was observed at lower pressure. The conversion of PLA was maximized at an oligomeric PLA molecular weight of ca. 1380. The yield of lactide increased but the fraction of D,L-lactide decreased with increasing molecular weight. The highest conversion with the lowest racemization degree was obtained at a catalyst concentration of 0.1 wt%. The lactide was more sensitive to racemization because of the entropic effect.

Keywords:poly(lactic acid);D,L-lactide;meso-lactide;catalysts;depolymerization;racemization;deprotonation

[References]

Mainilvarlet P, Rahm R, Gogolewski S, Biomaterials, 18, 257 (1997)
Hoogsteen W, Postema AR, Pennings AJ, Brinke GT, Macromolecules, 23, 634 (1990)
Bastioli C, Macromol. Symp., 135, 193 (1998)
Kim KW, Woo SI, Macromol. Chem. Phys., 203, 2245 (2002)
Moon SI, Lee CW, Miyamoto M, Kimura Y, J. Polym. Sci. A: Polym. Chem., 38(9), 1673 (2000)
Yamane K, USP 6916939 (2005)
Kohn FE, Van Den Berg JWA, Ridder VD, Feijen J, J. Appl. Polym. Sci., 29, 4265 (1984)
Shin GI, Kim JH, Kim SH, Kim YH, Korea Polym. J., 5(1), 19 (1997)
Nijenhuis AJ, Grijpma DW, Pennings AJ, Macromolecules, 25, 6419 (1992)
Zhang J, Gan Z, Zhong Z, Jing X, Polym. Int., 45, 60 (1998)
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Thakur KAM, Kean RT, Hall ES, Anal. Chem., 69, 4303 (1997)
Gruber PR, USP 2574073 (1993)
Kricheldorf HR, Serra A, Polym. Bull., 14, 497 (1985)
Kricheldorf HR, Sumbel M, Eur. Polym. J., 25, 585 (1989)
Witzke DR, Narayan R, Kolstad JJ, Macromolecules, 30(23), 7075 (1997)
Kricheldorf HR, Lee SR, Polymer, 36(15), 2995 (1995)
Yoo DK, Kim D, Lee DS, Macromol. Res., 13(1), 68 (2005)
Benecke HP, USP5332839 (1994)
Muller M, USP 5214159 (1993)
Kricheldorf HR, Kreiser-Saunders I, Macromol. Chem., 191, 1057 (1990)
Kricheldorf HR, Kreisersaunders I, Boettcher C, Polymer, 36(6), 1253 (1995)
Kricheldorf HR, Damaru DO, Macromol. Chem., 198, 1753 (1997)
Tsuji H, Fukui I, Daimon H, Fujie K, Polym. Degrad. Stabil., 81, 501 (2003)

[Referenced By]

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[2] Hoogsteen W, Postema AR, Pennings AJ, Brinke GT, Macromolecules, 23, 634 (1990)

[3] Bastioli C, Macromol. Symp., 135, 193 (1998)

[4] Kim KW, Woo SI, Macromol. Chem. Phys., 203, 2245 (2002)

[5] Moon SI, Lee CW, Miyamoto M, Kimura Y, J. Polym. Sci. A: Polym. Chem., 38(9), 1673 (2000)

[6] Yamane K, USP 6916939 (2005)

[7] Kohn FE, Van Den Berg JWA, Ridder VD, Feijen J, J. Appl. Polym. Sci., 29, 4265 (1984)

[8] Shin GI, Kim JH, Kim SH, Kim YH, Korea Polym. J., 5(1), 19 (1997)

[9] Nijenhuis AJ, Grijpma DW, Pennings AJ, Macromolecules, 25, 6419 (1992)

[10] Zhang J, Gan Z, Zhong Z, Jing X, Polym. Int., 45, 60 (1998)

[11] Thakur KA, Kean RT, Hall ES, Kolstad JJ, Lindgren TA, Doscotch MA, Siepmann JI, Munson EJ, Macromolecules, 30(8), 2422 (1997)

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[13] Gruber PR, USP 2574073 (1993)

[14] Kricheldorf HR, Serra A, Polym. Bull., 14, 497 (1985)

[15] Kricheldorf HR, Sumbel M, Eur. Polym. J., 25, 585 (1989)

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[20] Muller M, USP 5214159 (1993)

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[23] Kricheldorf HR, Damaru DO, Macromol. Chem., 198, 1753 (1997)

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