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Synthesis of partially biobased polymer-bearing reactive epoxy groups in the side chains by radical copolymerization of limonene oxide with methyl acrylate

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Abstract

A radical copolymerization behavior of limonene oxide and methylacrylate was investigated, by which a partially biobased polymer-bearing reactive epoxy groups in the side chains was obtained in 43 % yield in the maximum. Degree of LO incorporation into the copolymer was determined to be 34–37 % when 5.0 mol % of 2,2′-azobis(isobutyronitrile) was employed, despite initial feed ratios. Reactivity of the epoxy groups in the side chains was investigated by two different methods. One is ring-opening of the epoxy groups with benzyl thiol, giving the corresponding polymer with β-hydroxyl sulfide moieties in 95 % yield. Another one is hydrolyzation of the epoxy groups in HCl aqueous solution at room temperature, providing a quantitative formation of the dihydroxyl groups in the side chains.

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References

  1. Gandini A (2008) Polymers from renewable resources: a challenge for the future of macromolecular materials. Macromolecules 41(24):9491–9504

    Article  CAS  Google Scholar 

  2. Mathers RT (2012) How well can renewable resources mimic commodity monomers and polymers? J Polym Sci A 50:1–15

    Article  CAS  Google Scholar 

  3. Zhao J, Schlaad H (2012) Synthesis of terpene-based polymers. Adv Polym Sci 253:151–190

    Google Scholar 

  4. Kawahara S, Suksawad P, Yamamoto Y, Kuroda H (2009) Nanomatrix channel for ionic molecular transportation. Macromolecules 42:8557–8560

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

  6. Dash M, Chiellini F, Ottenbrite RM, Chiellini E (2011) Chitosan—a versatile semi-synthetic polymer in biomedical applications. Prog Polym Sci 36:981–1014

    Article  CAS  Google Scholar 

  7. Södergård A, Stolt M (2002) Properties of lactic acid based polymers and their correlation with composition. Prog Polym Sci 27(6):1123–1163

    Article  Google Scholar 

  8. Rasal RM, Janorkar AV, Hirt DE (2010) Poly(lactic acid) modifications. Prog Polym Sci 35(3):338–356

    Article  CAS  Google Scholar 

  9. Harish Prashanth KV, Tharanathan RN (2007) Chitin/chitosan: modifications and their unlimited application potential—an overview. Trends Food Sci Technol 18:117–131

    Article  Google Scholar 

  10. Rinaudo M (2006) Chitin and chitosan: properties and applications. Prog Polym Sci 31(7):603–632

    Article  CAS  Google Scholar 

  11. Vepari C, Kaplan DL (2007) Silk as a biomaterial. Prog Polym Sci 32:991–1007

    Article  CAS  Google Scholar 

  12. Marín FR, Soler-Rivas C, Benavente-García O, Castillo J, Pérez-Alvarez JA (2007) By-products from different citrus processes as a source of customized functional fibres. Food Chem 100(2):736–741

    Article  Google Scholar 

  13. Lan-Phi NT, Shimamura T, Ukeda H, Sawamura M (2009) Chemical and aroma profiles of yuzu (Citrus junos) peel oils of different cultivars. Food Chem 115:1042–1047

    Article  Google Scholar 

  14. Terada A, Kitajima N, Machmudah S, Tanaka M, Sasaki M, Goto M (2010) Cold-pressed yuzu oil fractionation using countercurrent supercritical CO2 extraction column. Sep Purif Technol 71:107–113

    Article  CAS  Google Scholar 

  15. Oliveira P, Rojas-Cervantes ML, Ramos AM, Fonseca IM, Botelho do Rego AM, Vital J (2006) Limonene oxidation over V2O5/TiO2 catalysts. Catal Today 118:307–314

    Article  CAS  Google Scholar 

  16. Yadav JS, Reddy BVS, Baishya G (2002) InCl3-catalyzed highly regioselective ring opening of epoxides with thiols. Chem Lett 9:906–907

    Article  Google Scholar 

  17. Satoh K, Matsuda M, Nagai K, Kamigaito M (2010) AAB-sequence living radical chain copolymerization of naturally occurring limonene with maleimide: an end-to-end sequence-regulated copolymer. J Am Chem Soc 132:10003–10005

    Article  CAS  Google Scholar 

  18. Sharma S, Srivastava AK (2004) Synthesis and characterization of a terpolymer of limonene, styrene, and methyl methacrylate via a free-radical route. J Appl Polym Sci 91:2343–2347

    Article  CAS  Google Scholar 

  19. Kennedy JP (1975) Cationic polymerization of olefins: a critical inventory. Wiley, New York

    Google Scholar 

  20. Doiuchi T, Yamaguchi H, Minoura Y (1981) Cyclocopolymerization of d-limonene with maleic anhydride. Eur Polym J 17:961–968

    Article  CAS  Google Scholar 

  21. Maślińska-Solich J, Kupka T, Kluczka M (1994) Optically active polymers, 2. Copolymerization of limonene with maleic anhydride. Macromol Chem Phys 195:1843–1850

    Article  Google Scholar 

  22. Sharma S, Srivastava AK (2003) Alternating copolymers of limonene with methyl methacrylate: kinetics and mechanism. J Macromol Sci A 40:593–603

    Google Scholar 

  23. Sharma S, Srivastava AK (2004) Synthesis and characterization of copolymers of limonene with styrene initiated by azobisisobutyronitrile. Eur Polym J 40:2235–2240

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was partly supported by grants from the Circle for the Promotion of Science and Engineering, and from Kogin Regional Economy Promotion Foundation.

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Authors and Affiliations

  1. Department of Materials Science and Engineering, Kochi National College of Technology, 200-1, Monobe otsu, Nankoku, Kochi, 783-8508, Japan

    Hisatoyo Morinaga, Yoshihide Kiyokawa, Mei Kataoka & Junya Masuda

  2. Advanced Course in Materials Science and Engineering, Kochi National College of Technology, 200-1, Monobe otsu, Nankoku, Kochi, 783-8508, Japan

    Yoshihide Kiyokawa

  3. Department of Chemistry and Chemical Biology, Graduate School of Engineering, Gunma University, 1-5-1 Tenjin-cho, Kiryu, Gunma, 376-8515, Japan

    Daisuke Nagai

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  1. Hisatoyo Morinaga
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  2. Yoshihide Kiyokawa
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  3. Mei Kataoka
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  4. Junya Masuda
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  5. Daisuke Nagai
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Correspondence to Hisatoyo Morinaga.

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Morinaga, H., Kiyokawa, Y., Kataoka, M. et al. Synthesis of partially biobased polymer-bearing reactive epoxy groups in the side chains by radical copolymerization of limonene oxide with methyl acrylate. Polym. Bull. 70, 1113–1123 (2013). https://doi.org/10.1007/s00289-012-0890-z

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  • DOI: https://doi.org/10.1007/s00289-012-0890-z

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