Branched poly(lactide) synthesized by enzymatic polymerization: effects of molecular branches and stereochemistry on enzymatic degradation and alkaline hydrolysis.

作者: Keiji Numata , Rajiv K. Srivastava , Anna Finne-Wistrand , Ann-Christine Albertsson , Yoshiharu Doi

DOI: 10.1021/BM700537X

关键词: HydrolysisPolymer architectureMolar mass distributionRing-opening polymerizationOrganic chemistryPolymerStereochemistryChemistryAlkaline hydrolysis (body disposal)Polymer chemistryLactidePolymerization

摘要: In this article the effects of number molecular branches (chain ends) and stereochemistry poly(lactide)s (PLAs) on enzymatic degradation alkaline hydrolysis are studied. Various linear branched PLAs were synthesized using lipase PS (Pseudomonas fluorescens)-catalyzed ring-opening polymerization (ROP) lactide monomers having different stereochemistries (L-lactide, D-lactide, D,L-lactide). Five alcohols used as initiators for ROP, monomer-to-initiator molar feed ratio was varied from 10 to 100 1000 each branch in polymer architecture. The properties that would affect degradations, i.e., glass transition temperature, melting enthalpy, advancing contact angle, determined. PLA films degraded proteinase K or 1.0 M NaOH solution, weight loss changes average (Mn) studied during 12 h degradation. results suggest an increase enhances its degradability alkali hydrolyzability. Moreover, change Mn poly(L-lactide) (PLLA) by indicated decrease first place dependent thereafter length PLA. PLLA, poly(D-lactide) (PDLA), poly(D,L-lactide) (PDLLA) differed segment It is suggested PDLLA preferentially K.

参考文章(25)
Soo Hyun Kim, Yang-Kyoo Han, Young Ha Kim, Sung Ill Hong, Multifunctional initiation of lactide polymerization by stannous octoate/pentaerythritol Macromolecular Chemistry and Physics. ,vol. 193, pp. 1623- 1631 ,(1992) , 10.1002/MACP.1992.021930706
Anna Finne, Ann-Christine Albertsson, Controlled Synthesis of Star-Shaped l-Lactide Polymers Using New Spirocyclic Tin Initiators Biomacromolecules. ,vol. 3, pp. 684- 690 ,(2002) , 10.1021/BM020009O
Hans R. Kricheldorf, Heiko Hachmann-Thiessen, Gert Schwarz, Telechelic and star-shaped poly(L-lactide)s by means of bismuth(III) acetate as initiator Biomacromolecules. ,vol. 5, pp. 492- 496 ,(2004) , 10.1021/BM030064C
Harri Korhonen, Antti Helminen, Jukka V Seppälä, Synthesis of polylactides in the presence of co-initiators with different numbers of hydroxyl groups Polymer. ,vol. 42, pp. 7541- 7549 ,(2001) , 10.1016/S0032-3861(01)00150-1
Minna Hakkarainen, Sigbritt Karlsson, Ann-Christine Albertsson, Influence of low molecular weight lactic acid derivatives on degradability of polylactide Journal of Applied Polymer Science. ,vol. 76, pp. 228- 239 ,(2000) , 10.1002/(SICI)1097-4628(20000411)76:2<228::AID-APP12>3.0.CO;2-B
Michael S. Reeve, Stephen P. McCarthy, Milton J. Downey, Richard A. Gross, Polylactide stereochemistry: effect on enzymic degradability Macromolecules. ,vol. 27, pp. 825- 831 ,(1994) , 10.1021/MA00081A030
Chung Shih, Chain-end scission in acid catalyzed hydrolysis of poly (d,l-lactide) in solution Journal of Controlled Release. ,vol. 34, pp. 9- 15 ,(1995) , 10.1016/0168-3659(94)00100-9
A Zaks, A. Klibanov, Enzymatic catalysis in organic media at 100 degrees C Science. ,vol. 224, pp. 1249- 1251 ,(1984) , 10.1126/SCIENCE.6729453
Christian BETZEL, Gour P. PAL, Wolfram SAENGER, Three-dimensional structure of proteinase K at 0.15-nm resolution FEBS Journal. ,vol. 178, pp. 155- 171 ,(1988) , 10.1111/J.1432-1033.1988.TB14440.X