Abstract
This article briefly reviews research developments on “green polymer chemistry” and focuses on the studies recently performed by our group and related work by some other groups. The green character of polymer synthesis has been viewed from the standpoint of starting materials, polymerization catalyst, reaction solvent, and polymer recycling. Starting materials employ biobased renewable resources such as lactic acid (LA), itaconic anhydride (IAn), succinic anhydride, 1,4-butane diol, etc. Green catalysts include enzymes like lipase and protease. Green solvents are water, supercritical carbon dioxide, and ionic liquids; in particular, water is often used for emulsion systems. From LA and IAn, methacyloyl-polymerizable macromonomers were derived and their copolymerization with a (meth)acryroyl monomer in miniemulsion produced a graft copolymer having LA graft chains. The copolymers are classed as bioplastics from their biomass content (≥25 wt%) and are applicable for coatings. LA chain-containing comb polymers and a star-type polymer were prepared, the latter being currently employed as a coating material. The mechanism of catalysis of the enzymes in the oligomerization of LA alkyl esters was examined to reveal direct evidence that a deacylation step determines the enantioselection. Lipase catalysis was utilized for a polymer recycling system
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References
Anastas PT, Warner JC (1998) Green chemistry: theory and practice. Oxford University Press, Oxford
Vorvath IT, Anastas PT (2007) Innovations and green chemistry. Chem Rev 107:2169–2173
Narayan R (2006) Biobased and biodegradable polymer materials: rationale, drivers, and technology exemplars. In: Khemani KC, Scholz C (eds) Degradable polymers and materials. ACS Symposium Series vol 939. Chap 18, pp 282–306. American Chemical Society, Washington, D.C.
Coates GW, Hillmyer MA (2009) A virtual issue of macromolecules: polymers from renewable resources. Macromolecules 42:7987–7989
Bomgardner MM (2012) A summer of start-ups for biobased chemicals. Chem Eng News 90(38):10–15
Kobayashi S (1999) Enzymatic polymerization – polymer synthesis catalyzed by a natural macromolecule. High Polym Jpn 48:124–127
Kobayashi S (1999) Enzymatic polymerization: a new method of polymer synthesis. J Polym Sci A Polym Chem 37:3041–3056
Kobayashi S, Uyama H, Takamoto T (2000) Lipase-catalyzed degradation of polyesters in organic solvents. A new methodology of polymer recycling using enzyme as catalyst. Biomacromolecules 1:3–5
Sakamoto J, Sugiyama J, Kimura S, Imai T, Itoh T, Watanabe T, Kobayashi S (2000) Artificial chitin spherulites composed of single crystalline ribbons of α-chitin via enzymatic polymerization. Mcromolecules 33:4155–4160
Ikeda R, Tanaka H, Uyama H, Kobayashi S (2000) A new crosslinkable polyphenol from renewable resource. Macromol Rapid Commun 21:496–499
Higashimura H, Fujisawa K, Moro-oka Y, Namekawa S, Kubota M, Shiga A, Uyama H, Kobayashi S (2000) New crystalline polymers: poly(2,5-dialkyl-1,4-phenylene oxide)s. Macromol Rapid Commun 21:1121–1124
Ikeda R, Tanaka H, Oyabu H, Uyama H, Kobayashi S (2001) Preparation of artificial urushi via an environmentally benign process. Bull Chem Soc Jpn 74:1067–1073
Kobayashi S, Uyama H, Kimura S (2001) Enzymatic polymerization. Chem Rev 101:3793–3818
Kobayashi S, Uyama H, Ohmae M (2001) Enzymatic polymerization for precision polymer synthesis. Bull Chem Soc Jpn 74:613–635
Uyama H, Kuwabara M, Tsujimoto T, Nakano M, Usuki A, Kobayashi S (2003) Green nanocomposite from renewable resources: plant oil–clay hybrid materials. Chem Mater 15:2492–2494
Kobayashi S, Uyama H (2003) Enzymatic polymerization. In: Kroschwitz JI (ed) Encyclopedia of polymer science and technology, 3rd edn. Wiley, New York, pp 328–364
Kobayashi S, Ritter H, Kaplan D (eds) (2006) Enzyme-catalyzed synthesis of polymers. Adv Polym Sci 194
Kobayashi S, Ohmae M (2007) Polymer synthesis and modification by enzymatic catalysis. In: Matyjaszewski K, Gnanou Y, Leibler L (eds) Macromolecular engineering: precise synthesis, materials properties, applications, vol 10, Wiley-VCH, Weinheim., pp 400–477
Kobayashi S (2009) Recent developments in lipase-catalyzed synthesis of polyesters. Macromol Rapid Commun 30:237–266
Kobayashi S, Makino A (2009) Enzymatic polymer synthesis: an opportunity for green polymer chemistry. Chem Rev 109:5288–5353
Kobayashi S (2010) Lipase-catalyzed polyester synthesis − a green polymer chemistry. Proc Jpn Acad Ser B 86:338–365
Kobayashi S (2011) Green polymer synthesis using enzyme catalysts. In: Misono M, Murahashi S (eds) Green chemistry – chemistry for sustainable society. Kodansha Scientific, Tokyo, pp 192–203
Kobayashi S (2012) Enzymatic polymerization. In: Matyjaszewski K, Moeller M (eds) Polymer science: a comprehensive reference, vol 5. Elsevier, Amsterdam, pp 217-237
Puskas JE, Sen MY, Seo KS (2009) Green polymer chemistry using nature’s catalyst, enzyme. J Polym Sci A Polym Chem 47:2959–2976
Cheng HN, Gross RA (eds) (2010) Green polymer chemistry: biocatalysis and biomaterials. ACS Symposium Series, vol 1043. American Chemical Society, Washington, D.C.
Werpy T, Petersen G (2004) Top value added chemicals from biomass. The National Renewable Energy Laboratory and DOE National Laboratory, Oak Ridge
Tsuji H, Ikada Y (2000) Properties and morphology of poly(L-lactide) 4. Effects of structural parameters on long-term hydrolysis of poly(L-lactide) in phosphate-buffered solution. Polym Deg Stab 67:179–189
Moon SI, Lee CW, Miyamoto M, Kimura Y (2000) Melt polycondensation of L-lactic acid with Sn(II) catalysts activated by various proton acids: a direct manufacturing route to high molecular weight poly(L-lactic acid). J Polym Sci A Polym Chem 38:1673–1679
Moon S-I, Lee CW, Taniguchi I, Miyamoto M, Kimura Y (2001) Melt/solid polycondensation of L-lactic acid: an alternative route to poly(L-lactic acid) with high molecular weight. Polymer 42:5059–5062
Dechy-Cabaret O, Martin-Vaca B, Bourissou D (2004) Controlled ring-opening polymerization of lactide and glycolide. Chem Rev 104:6147–6176
Gupta B, Revagade N, Hilborn J (2007) Poly(lactic acid) fiber: an overview. Prog Polym Sci 32:455–482
Fukushima K, Chang YH, Kimura Y (2007) Enhanced stereocomplex formation of poly(L-lactic acid) and poly(D-lactic acid) in the presence of stereoblock poly(L-lactic acid). Macromol Biosci 7:829–835
Jiang X, Smith MR III, Baker GL (2008) Water-soluble thermoresponsive polylactides. Macromolecules 41:318–324
Chuma A, Hom HW, Swope WC, Pratt RC, Zhang L, Lohmeijer BG, Wade CG, Waymouth RM, Hedrick JL, Rice JE (2008) The reaction mechanism for the organocatalytic ring-opening polymerization of L-lactide using a guanidine-based catalyst: hydrogen-bonded or covalently bonded? J Am Chem Soc 130:6749–6759
Jing F, Hillmyer MA (2008) A bifunctional monomer derived from lactide for toughening polylactide. J Am Chem Soc 130:13826–13827
Pitet LM, Amendt MA, Hillmyer MA (2010) Nanoporous linear polyethylene from a block polymer precursor. J Am Chem Soc 132:8230–8231
Nishida H, Andou Y, Watanabe K, Arazoe Y, Ide S, Shirai Y (2011) Poly(tetramethyl glycolide) from renewable carbon, a racemization-free and controlled depolymerizable polyester. Macromolecules 44:12–13
Inkinen S, Hakkarainen M, Albertsson A-C, Södergård A (2011) From lactic acid to poly(lactic acid) (PLA): characterization and analysis of PLA and its precursor. Biomacromolecules 12:523–532
Stoclet G, Seguela R, Lefebvre JM, Li S, Vert M (2011) Thermal and strain-induced chain ordering in lactic acid stereocopolymers: influence on the composition in stereomers. Macromolecules 44:4961–4969
Shin EJ, Jones AE, Waymouth RM (2012) Stereocomplexation in cyclic and linear polylactide blends. Macromolecules 45:595–598
Ishimoto K, Arimoto M, Okuda T, Yamaguchi S, Aso Y, Ohara H, Kobayashi S, Ishii M, Morita K, Yamashita H, Yabuuchi N (2012) Biobased polymers: synthesis of graft copolymers and comb polymers using lactic acid macromonomer and properties of the product polymers. Biomacromolecules 13:3757–3768
Ishimoto K, Arimoto M, Ohara H, Kobayashi S, Ishii M, Morita K, Yamashita H, Yabuuchi N (2009) Biobased polymer system: miniemulsion of poly(alkyl methacrylate-graft-lactic acid)s. Biomacromolecules 10:2719–2723
Okuda T, Ishimoto K, Ohara H, Kobayashi S (2012) Renewable biobased polymeric materials: facile synthesis of itaconic anhydride-based copolymers with poly(L-lactic acid) grafts. Macromolecules 45:4166–4174
Morita K, Yamashita H, Yabuuchi N, Hayata Y, Ishii M, Ishimoto K, Ohara H, Kobayashi S (2011) Application of star-shaped poly(lactic acid)s to two component and UV-curable coatings. J Network Polym Jpn 32:192–196
Morita K, Yamashita H, Yabuuchi N, Hayata Y, Ishii M, Ishimoto K, Ohara H, Kobayashi S (2011) Synthesis of star-shaped oligomeric lactic acids with reactive double bonds and their application to UV curable coatings. In: Proceedings of RadTech Asia 2011. RadTech Japan, Tokyo, pp 126–129
Palmans ARA, Heise A (eds) (2011) Enzymatic polymerisation. Adv Polym Sci 237
Uyama H, Kobayashi S (1993) Enzymatic ring-opening polymerization of lactones catalyzed by lipase. Chem Lett 1149–1150
Uyama H, Takeya K, Kobayashi S (1993) Synthesis of polyesters by enzymatic ring-opening copolymerization using lipase catalyst. Proc Jpn Acad B 69:203–207
Knani D, Gutman AL, Kohn DH (1993) Enzymatic polyesterification in organic media – enzyme-catalyzed synthesis of linear polyesters. 1. Condensation polymerization of linear hydroxyesters. 2. Ring-opening polymerization of ε-caprolactone. J Polym Sci A Polym Chem 31:1221–1232
Yamaguchi S, Tanha M, Hult A, Okuda T, Ohara H, Kobayashi S (2013) Green polymer chemistry: lipase-catalyzed synthesis of bio-based reactive polyesters employing itaconic anhydride as renewable monomer. Polym J doi:10.1038/pj.2013.62
Kobayashi S, Uyama H (1993) Enzymatic polymerization of cyclic acid anhydrides and glycols by a lipase catalyst. Macromol Chem Rapid Commun 14:841–844
Bonduelle C, Martin-Vaca B, Bourissou D (2009) Lipase-catalyzed ring-opening polymerization of the O-carboxylic anhydride derived from lactic acid. Biomacromolecules 10:3069–3073
Ohara H, Onogi A, Yamamoto M, Kobayashi S (2010) Lipase-catalyzed oligomerization and hydrolysis of alkyl lactates: direct evidence in the catalysis mechanism that enantioselection is governed by a deacylation step. Biomacromolecules 11:2008–2015
Ohara H, Nishioka E, Yamaguchi S, Kawai F, Kobayashi S (2011) Protease-catalyzed oligomerization and hydrolysis of alkyl lactates involving L-enantioselective deacylation step. Biomacromolecules 12:3833–3837
Hans M, Keul H, Moeller M (2009) Ring-opening polymerization of DD-lactide catalyzed by Novozyme 435. Macromol Biosci 9:239–247
Ohara H, Yamamoto M, Onogi A, Hirao K, Kobayashi S (2011) Optical resolution of n-butyl D- and L-lactates using immobilized lipase catalyst. J Biosci Bioeng 111:19–21
Hedstrom L (2002) Serine protease mechanism and specificity. Chem Rev 102:4501–4524
Kawai F, Nakadai K, Nishioka E, Nakajima H, Ohara H, Masaki K, Iefuji H (2011) Different enantioselectivity of two types of poly(lactic acid) depolymerases toward poly(L-lactic acid) and poly(D-lactic acid). Polym Deg Stab 96:1342–1348
Wilmouth RC, Clifton IJ, Robinson CV, Roach PL, Alpin RT, Westwood NJ, Hajdu J, Schofield CJ (1997) Structure of a specific acyl-enzyme complex formed between β-casomorphin-7 and porcine pancreatic elastase. Nat Struc Biol 4:456–462
Ollis DL, Cheah E, Cygler M, Dijkstra B, Frolow F, Franken SM, Harel M, Remington SJ, Silman I, Schrag J, Sussman JL, Vershueren KHG, Goldman A (1992) The α/β hydrolase fold. Protein Eng 5:197–211
Borén L, Martín-Matute B, Xu Y, Córdova A, Bäeckvall J-E (2006) (S)-selective kinetic resolution and chemoenzymatic dynamic resolution of secondary alcohols. Chem Eur J 12:225–232
Ebata H, Toshima K, Matsumura S (2000) Lipase-catalyzed transformation of poly(ε-caprolactone) into cyclic dicaprolactone. Biomacromolecules 1:511–551
Okajima S, Kondo R, Toshima K, Matsumura S (2003) Lipase-catalyzed transformation of poly(butylene adipate) and poly(butylene succinate) into polymerizable cyclic oligomers. Biomacromolecules 4:1514–1519
Takahashi Y, Okajima S, Toshima K, Matsumura S (2004) Lipase-catalyzed transformation of poly(lactic acid) into cyclic oligomers. Macromol Biosci 4:346–353
Osanai Y, Toshima K, Matsumura S (2003) Enzymatic degradation of poly(R, S-3-hydroxybutanonoate) to cyclic oligomers under continuous flow. Green Chem 5:567–570
Matsumura S (2007) Enzymatic synthesis of polyesters via ring-opening polymerization. Adv Polym Sci 194:95–132
Numata K, Srivastava RK, Finne-Wistrand A, Albertsson A-C, Doi Y, Abe H (2007) Branched poly(lactide) synthesized by enzymatic polymerization: effect of molecular branches and stereochemistry on enzymatic degradation and alkaline hydrolysis. Biomacromolecules 8:3115–3125
Lecomte P, Jerome C (2012) Recent developments in ring-opening polymerization of lactones. Adv Polym Sci 245:173–218
Namekawa S, Uyama H, Kobayashi S (1998) Lipase-catalyzed ring-opening polymerization of lactones in water. Polym J 30:269–271
Kobayashi S, Uyama H, Namekawa S (1998) In vitro biosynthesis of polyesters with isolated enzymes in aqueous systems and organic solvents. Polym Deg Stab 59:195–201
Uyama H, Takeya K, Kobayashi S (1995) Enzymatic ring-opening polymerization of lactones to polyesters by lipase catalyst: unusually high reactivity of macrolides. Bull Chem Soc Jpn 68:56–61
Taden A, Antonietti M, Landfester K (2003) Enzymatic polymerization toward biodegradable polyester nanoparticles. Macromol Rapid Commun 24:512–516
Takamoto T, Uyama H, Kobayashi S (2001) Lipase-catalyzed synthesis of aliphatic polyesters in supercritical carbon dioxide. e-Polymers 4:1–6
Loeker FC, Duxbury CJ, Kumar R, Gao W, Gross RA, Howdle SM (2004) Enzyme-catalyzed ring-opening polymerization of ε-caprolactone in supercritical carbon dioxide. Macromolecules 37:2450–2453
Takamoto T, Uyama H, Kobayashi S (2001) Lipase-catalyzed degradation of polyester in supercritical carbon dioxide. Macromol Biosci 1:215–218
Kubisa P (2005) Ionic liquids in the synthesis and modification of polymers. J Polym Sci A Polym Chem 43:4675–4683
Uyama H, Takamoto T, Kobayashi S (2002) Enzymatic synthesis of polyesters in ionic liquids. Polym J 34:94–96
Marcilla R, de Jeus M, Mecerreyes D, Duxbury CJ, Koning CE, Heise A (2006) Enzymatic polyester synthesis in ionic liquids. Eur Polym J 42:1215–1221
Yoshizawa-Fujita M, Saito C, Takeoka Y, Rikukawa M (2008) Lipase-catalyzed polymerization of L-lactide in ionic liquids. Polym Adv Technol 19:1396–1400
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Kobayashi, S. (2013). Green Polymer Chemistry: Recent Developments. In: Percec, V. (eds) Hierarchical Macromolecular Structures: 60 Years after the Staudinger Nobel Prize II. Advances in Polymer Science, vol 262. Springer, Cham. https://doi.org/10.1007/12_2013_236
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DOI: https://doi.org/10.1007/12_2013_236
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