High molecular weight poly (L-(+)-lactic acid)s are generally prepared by ROP of cyclic dimer, L-lactide, which is a crystalline solid. This involves conversion.

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Presentation transcript:

High molecular weight poly (L-(+)-lactic acid)s are generally prepared by ROP of cyclic dimer, L-lactide, which is a crystalline solid. This involves conversion of an aqueous solution of L-lactic acid to a dimer, followed by its purification and polymerization. It would be desirable to have a non aqueous precursor to poly(L-lactic acid), which is relatively less volatile and is capable of efficient step growth polymerization. Simple alkyl esters of L-(+)-Lactic acid are not very useful because of their high volatility under conditions normally employed for step growth reactions. Such a monomer or precursor will also enable synthesis of copolymers of L-lactic acid/esters with α, ω-hydroxyl ester compounds, many of which are naturally available. Mr. Yogesh Nevare is thankful to DST, New Delhi for financial support. The assistance of Dr. P. R. Rajamohanan, CSIR-NCL for NMR analysis is gratefully acknowledged. Objectives Synthesis Acknowledgement High molecular weight Poly(L-Lactic acid)s and their copolymers by polycondensation: Is it Possible ? Yogesh R. Nevare, Bhaskar B. Idage, Susheela B. Idage, Swaminathan Sivaram* Polymer Science and Engineering Division, National Chemical Laboratory, Pune – 411 008 Email: s.sivaram@ncl.res.in; yr.nevare@ncl.res.in Structure and composition of 1 Structure and composition of 3 Tg Tc Tm Future work DSC thermogram of 4. Structure and composition of 4 MALDI-TOF-MS spectra of 4. 1H NMR Spectrum of 4 in DMSO-d6. M. Vert et. al.; Macromolecules, 29, 3535 (1996). 1H NMR Spectrum of 1 in DMSO-d6. Structure and composition of 2 1H NMR Spectrum of 2 in DMSO-d6 . 1H NMR Spectrum of 3 in DMSO-d6 (DP= 4.75). 14mer 15mer 16mer 17mer 18mer 19mer 20mer 21mer 22mer 23mer 24mer 25mer 26mer 27mer 28mer 29mer 30mer 31mer 34mer 35mer 8mer 41mer 43mer 4mer 5mer 6mer 7mer 9mer 10mer 11mer 12mer 13mer m/z a b c, f, j d, g h, i, e e h, i a’ c’ f’ j’ b’ d’ g’ e’ h’ i’ k’ h’ i’ e’ To examine the kinetics of transesterification Vs cyclic dimer formation using 3 as the precursor and comparison with polymerization of aqueous L-lactic acid. To establish the structure of polymers in terms of composition and end groups. To examine the effect of structural variation of 3 as relative rates of chain growth and cyclization. Synthesis of a novel AB precursor for preparation of Poly(l-lactic acid ester)s. Aqueous L-(+)-lactic acid can be extracted into a CH2Cl2 solution. The organic solution of L-(+)-lactic acid has DP= 1.76. L-(+)-lactic acid, commercial procured, is a mixture of monomer and higher oligomers with an DP=1.45. Formation of the AB precursor with a DP= 2.33 which confirming the addition of 1 methyl lactate unit. AB precursor 3 undergoes further chain extension under step growth polymerization conditions. However, this is accompanied with the formation of ~ 20 % L-lactide 5.