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Synthesis of poly(lactic acid) by heterogeneous acid catalysis from d,l-lactic acid

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Abstract

Poly(lactic acid) (PLA) is an important polymer because of its significant biocompatibility and biodegradability. Supported H3PW12O40 (H3PW) on activated carbon was utilized for the catalytic polymerization of D,L-lactic acid, resulting in blends of PLA. The stability of the polymer was monitored by thermogravimetry (TGA), and the decomposition temperature (Td) was used to determine the optimal production conditions (i.e., temperature of 180 °C for 15 h; 0.1 wt. % catalyst; 20 wt. % H3PW/carbon calcined at 400 °C). The best catalyst was reused three times with good activity and recovery (95 %) and was analyzed to confirm the consistency of its Keggin structure, dispersion, and acidity, which are important parameters that affect the catalyst’s activity. The obtained polymer was characterized by gel permeation chromatography (GPC), Fourier-transform infrared spectroscopy (FT-IR), 1H/13C nuclear magnetic resonance (NMR) spectroscopy, specific optical rotation ([α]D 25), powder X-ray diffraction (XRD), and differential scanning calorimetry (DSC). The average molar mass of the polymer was 17,400 g mol−1. Blends of poly(lactic acid) with 85 % poly(L-lactic acid) stereospecific isomer were obtained.

Stereoselective synthesis of 85 % PLLA from polymerization of d,l-lactic acid using 12-tungstophosphoric acid supported on carbon as a catalyst

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References

  1. Dusselier M, Van Wouwe P, Dewaele A, Makshina E, Sels BF (2013) Lactic acid as a platform chemical in the biobased economy: the role of chemocatalysis. Energy Environ Sci 6:1415–1442

    Article  CAS  Google Scholar 

  2. Inkinen S, Hakkarainen M, Albertsson A, Sodergard A (2011) From lactic acid to poly(lactic acid) (PLA): characterization and analysis of PLA and its precursors. Biomacromolecules 12:523–532

    Article  CAS  Google Scholar 

  3. Garlotta DJ (2001) A literature review of poly(lactic acid). J Polym Environ 9:63–84

    Article  CAS  Google Scholar 

  4. Sodergard A, Stolt M (2002) Properties of lactic acid based polymers and their correlation with composition. Prog Polym Sci 27:1123–1163

    Article  CAS  Google Scholar 

  5. Bendix D (1998) Chemical synthesis of polylactide and its copolymers for medical applications. Polym Degrad Stab 59:129–135

    Article  CAS  Google Scholar 

  6. Lunt J (1998) Large-scale production, properties and commercial applications of polylactic acid polymers. Polym Degrad Stab 59:145–152

    Article  CAS  Google Scholar 

  7. Auras R, Harte B, Selke S (2004) An overview of polylactides as packaging materials. Macromol Biosci 4:835–864

    Article  CAS  Google Scholar 

  8. Lee SY, Valtchev P, Dehghani F (2012) Synthesis and purification of poly(L-lactic acid) using a one step benign process. Green Chem 14:1357–1366

    Article  CAS  Google Scholar 

  9. Ren H, Ying H, Ouyang P, Xu P, Liu J (2013) Catalyzed synthesis of poly(l-lactic acid) by macroporous resin Amberlyst-15 composite lactate utilizing melting polycondensation. J Mol Catal A Chem 366:22–29

    Article  CAS  Google Scholar 

  10. Nampoothiri KM, Nair NR, John RP (2010) An overview of the recent developments in polylactide (PLA) research. Bioresour Technol 101:8493–8501

    Article  Google Scholar 

  11. Carrasco F, Gámez-Pérez J, Santana OO, Maspoch ML (2011) Processing of poly(lactic acid)/organomontmorillonite nanocomposites: microstructure, thermal stability and kinetics of the thermal decomposition. Chem Eng J 178:451–460

    Article  CAS  Google Scholar 

  12. Li W, Xu Z, Chen L, Shan M, Tian X, Yang C, Lv H, Qian X (2014) A facile method to produce graphene oxide-g-poly(L-lactic acid) as an promising reinforcement for PLLA nanocomposites. Chem Eng J 237:291–299

    Article  CAS  Google Scholar 

  13. Zhang L, Li Y, Wang H, Qiao Y, Chen J, Cao S (2015) Strong and ductile poly(lactic acid) nanocomposite films reinforced with alkylated graphene nanosheets. Chem Eng J 264:538–546

    Article  CAS  Google Scholar 

  14. Ovitt TM, Coates GW (2000) Stereoselective ring-opening polymerization of rac-lactide with a single-site, racemic aluminum alkoxide catalyst: synthesis of stereoblock poly(lactic acid). J Polym Sci A Polym Chem 38:4686–4692

    Article  CAS  Google Scholar 

  15. Sarasua J-R, Prud’homme RE, Wisniewski M, Le Borgne A, Spassky N (1998) Crystallization and melting behavior of polylactides. Macromolecules 31:3895–3905

    Article  CAS  Google Scholar 

  16. Jarmelo S, Marques DAS, Simões PN, Carvalho RA, Batista CMSG, Araujo-Andrade C, Gil MH, Fausto R (2012) Experimental (IR/Raman and 1H/13C NMR) and theoretical (DFT) studies of the preferential conformations adopted by l-lactic acid oligomers and poly(l-lactic acid) homopolymer. J Phys Chem B 116:9–21

    Article  CAS  Google Scholar 

  17. Peng B, Xu Y, Hu J, Bu Z, Wu L, Li B-G (2013) Synthesis of poly(l-lactic acid) with improved thermal stability by sulfonic acid-catalyzed melt/solid polycondensation. Polym Degrad Stab 98:1784–1789

    Article  CAS  Google Scholar 

  18. Lasprilla AJR, Martinez GAR, Lunelli BH, Jardini AL, Filho RM (2012) Poly-lactic acid synthesis for application in biomedical devices - a review. Biotechnol Adv 30:321–328

    Article  CAS  Google Scholar 

  19. Ovitt TM, Coates GW (1999) Stereoselective ring-opening polymerization of meso-lactide: synthesis of syndiotactic poly(lactic acid). J Am Chem Soc 121:4072–4073

    Article  CAS  Google Scholar 

  20. Cheng M, Attygalle AB, Lobkovsky EB, Coates GW (1999) Single-site catalysts for ring-opening polymerization: synthesis of heterotactic poly(lactic acid) from rac-lactide. J Am Chem Soc 121:11583–11584

    Article  CAS  Google Scholar 

  21. Radano CP, Baker GL, Smith MR (2000) Stereoselective polymerization of a racemic monomer with a racemic catalyst: direct preparation of the polylactic acid stereocomplex from racemic lactide. J Am Chem Soc 122:1552–1553

    Article  CAS  Google Scholar 

  22. Du H, Velders AH, Dijkstra PJ, Zhong Z, Chen X, Feijen J (2009) Polymerization of lactide using achiral bis(pyrrolidene) Schiff base aluminum complexes. Macromolecules 42:1058–1066

    Article  CAS  Google Scholar 

  23. Hancock SL, Mahon MF, Jones MD (2013) Monomeric Ti(IV) homopiperazine complexes and their exploitation for the ring opening polymerisation of rac-lactide. Chem Cent J 7(135):1–9

    Google Scholar 

  24. Motta AC, Duek EAR (2007) Síntese e caracterização do copolímero poli(L-co-D, L ácido láctico). Polímeros Ciência e Tecnologia 17:123–129

    Article  CAS  Google Scholar 

  25. Kaitian X, Kozluca A, Denkbas EB, Piskin E (1996) Poly (D, L-Lactic acid) homopolymers: synthesis and characterization. Turk J Chem 20:43–53

    CAS  Google Scholar 

  26. Fukushima K, Kimura Y (2006) Stereocomplexed polylactides (Neo-PLA) as high-performance bio-based polymers: their formation, properties, and application. Polym Int 55:626–642

    Article  CAS  Google Scholar 

  27. Rasal RM, Janorkar AV, Hirt DE (2010) Poly(lactic acid) modifications. Prog Polym Sci 35:338–356

    Article  CAS  Google Scholar 

  28. Reinoso FR (1998) The role of carbon materials in heterogeneous catalysis. Carbon 36:159–175

    Article  Google Scholar 

  29. Dupont P, Lefebvre F (1996) Esterification of propanoic acid by butanol and 2-ethylhexanol catalyzed by heteropolyacids pure or supported on carbon. J Mol Catal A Chem 114:299–307

    Article  CAS  Google Scholar 

  30. Schwegler MA, Vinke P, Van der Eijk M, Van Bekkum H (1992) Activated carbon as a support for heteropolyanion catalysts. Appl Catal A 80:41–57

    Article  CAS  Google Scholar 

  31. Dias JA, Rangel MC, Dias SCL, Caliman E, Garcia FAC (2007) Benzene transalkylation with C9+ aromatics over supported 12-tungstophosphoric acid on silica catalysts. Appl Catal A 328:189–194

    Article  CAS  Google Scholar 

  32. Caliman E, Dias JA, Dias SCL, Garcia FAC, de Macedo JL, Almeida LS (2010) Preparation and characterization of H3PW12O40 supported on niobia. Microporous Mesoporous Mater 132:103–111

    Article  CAS  Google Scholar 

  33. Oliveira CF, Dezaneti LM, Garcia FAC, de Macedo JL, Dias JA, Dias SCL, Alvim KSP (2010) Esterification of oleic acid with ethanol by 12-tungstophosphoric acid supported on zirconia. Appl Catal A 372:153–161

    Article  CAS  Google Scholar 

  34. Lee SW, Wang S (2006) Biodegradable polymers/bamboo fiber biocomposite with bio-based coupling agent. Compos Part A 37:80–91

    Article  CAS  Google Scholar 

  35. Dias JA, Osegovic JP, Drago RS (1999) The solid acidity of 12-tungstophosphoric acid. J Catal 183:83–90

    Article  CAS  Google Scholar 

  36. Dias JA, Dias SCL, Kob NE (2001) Dehydration of 1-propanol using H3PW12O40 as catalyst. J Chem Soc Dalton Trans 3:228–231

    Article  Google Scholar 

  37. Ding L, Jin W, Chu Z, Chen L, Lu X, Yuan G, Song J, Fan D, Bao F (2011) Bulk solvent-free melt ring-opening polymerization (ROP) of L-lactide catalyzed by Ni(II) and Ni(II)–Ln(III) complexes based on the acyclic Salen-type Schiff-base ligand. Inorg Chem Commun 14:1274–1278

    Article  CAS  Google Scholar 

  38. Prifts D, Petzetakis N, Sakellariou G, Pitsikalis M, Baskaran D, Mays JW, Hadjichristidis N (2009) Surface-initiated titanium-mediated coordination polymerization from catalyst-functionalized single and multiwalled carbon nanotubes. Macromolecules 42:3340–3346

    Article  Google Scholar 

  39. Espartero JL, Rashkov I, Li SM, Manolova N, Vert M (1996) NMR analysis of low molecular weight poly(lactic acid)s. Macromolecules 29:3535–3539

    Article  CAS  Google Scholar 

  40. Motta AC, Duek EAR (2006) Síntese, Caracterização e Degradação “in vitro” do Poli(L-ácido láctico). Polímeros Ciência e Tecnologia 16:26–32

    Article  CAS  Google Scholar 

  41. Yi Q, Wen X, Li L, He B, Nie Y, Wu Y, Zhang Z, Gu Z (2009) The chiral effects on the responses of osteoblastic cells to the polymeric substrates. Eur Polym J 45:1970–1978

    Article  CAS  Google Scholar 

  42. Bigg DM (1996) Effect of copolymer ratio on the crystallinity and properties of polylactic acid copolymers. Society of Plastics Engineers - Annual Technical Conference 54: 2028–2039

  43. Auras R, Lim L-T, Selke SEM, Tsuji H (2010) Poly(Lactic Acid): synthesis, structures, properties, processing, and applications. Wiley, New Jersey

    Book  Google Scholar 

Download references

Acknowledgments

We acknowledge Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) for research and doctorate scholarships and the financial support provided by Universidade de Brasília/Decanato de Pesquisa e Pós-Graduação/Instituto de Química (UnB/DPP/IQ), Ministério da Ciência, Tecnologia e Inovação/CNPq (MCT/CNPq), CAPES, Fundação de Empreendimentos Científicos e Tecnológicos (FINATEC), Fundação de Amparo a Pesquisa do Distrito Federal (FAPDF), Financiadora de Estudos e Projetos/Fundo de Infraestrutura (FINEP/CTInfra) and PETROBRAS. In addition, we wish to thank Prof. Dr. Nágila M. P. S. Ricardo for the GPC measurements performed at the Max Planck Institute for Polymer Research and Prof. Dr. Inês S. Resck and MSc. Luiz Eduardo C. Benedito for the 1H and 13C NMR measurements performed at Laboratório de Ressonância Magnética Nuclear (LRMN-IQ/UnB).

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Correspondence to José A. Dias.

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Chafran, L.S., Campos, J.M.C., Santos, J.S. et al. Synthesis of poly(lactic acid) by heterogeneous acid catalysis from d,l-lactic acid. J Polym Res 23, 107 (2016). https://doi.org/10.1007/s10965-016-0976-7

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