Syntheses of 2,6-O-alkyl celluloses: influence of methyl and ethyl groups regioselectively introduced at O-2 and O-6 positions on their solubility
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Abstract
2,6-Di-O-ethyl (2E6E) (1), 2-O-ethyl-6-O-methyl (2E6M) (2), and 6-O-ethyl-2-O-methyl (6E2M) (3) celluloses were synthesized via ring-opening polymerization of glucose orthopivalate derivatives. 2,6-Di-O-methyl cellulose (2M6M) was insoluble in any common solvents, though it was not expected. On the other hand, cellulose derivative 1 (2E6E) was soluble in chloroform. Introduced positions of alkyl groups on cellulose affected solubilities of cellulose derivatives. Their solubility in chloroform decreased in the order: polymer 1 (2E6E) > polymer 2 (2E6M) > polymer 3 (6E2M) ≫ 2M6M.
Keywords
Glucose orthopivalate Ring-opening polymerization 2,6-O-alkyl cellulose SolubilityNotes
Acknowledgments
This investigation was supported in part by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science, and Culture of Japan (No. 18680009).
References
- Erler U, Mischnick P, Stein A, Klemm D (1992) Determination of the substitution patterns of cellulose methyl ethers by HPLC and GLC—comparison of methods. Polym Bull 29(3–4):349–356. doi: https://doi.org/10.1007/BF00944830 CrossRefGoogle Scholar
- Gallardo V, Garcia ME, Ruiz MA (2001) Design, synthesis and characterisation of ethylcellulose latex. Macromol Chem Phys 202(11):2412–2416. doi: https://doi.org/10.1002/1521-3935(20010701)202:11<2412::AID-MACP2412>3.0.CO;2-5 CrossRefGoogle Scholar
- Heymann E (1935) Studies on sol-gel transitions. 1. The inverse sol-gel transformation of methylcellulose in water. Trans Faraday Soc 31:846. doi: https://doi.org/10.1039/tf9353100846 CrossRefGoogle Scholar
- Isogai A, Ishizu A, Nakano J (1986) Preparation of tri-O-alkylcelluloses by the use of a nonaqueous cellulose solvent and their physical characteristics. J Appl Polym Sci 31(2):341–352. doi: https://doi.org/10.1002/app.1986.070310205 CrossRefGoogle Scholar
- Kamitakahara H, Hori M, Nakatsubo F (1996) Substituent effect on ring-opening polymerization of regioselectively acylated α-D-glucopyranose 1,2,4-orthopivalate derivatives. Macromolecules 29(19):6126–6131. doi: https://doi.org/10.1021/ma960488h CrossRefGoogle Scholar
- Kamitakahara H, Koschella A, Mikawa Y, Nakatsubo F, Heinze T, Klemm D (2008) Syntheses and comparison of 2,6-di-O-methyl celluloses from natural and synthetic celluloses. Macromol Biosci 8(7):690–700. doi: https://doi.org/10.1002/mabi.200700291 CrossRefGoogle Scholar
- Klemm D, Heublein B, Fink HP, Bohn A (2005) Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem Int Ed 44(22):3358–3393. doi: https://doi.org/10.1002/anie.200460587 CrossRefGoogle Scholar
- Nakatsubo F, Kamitakahara H, Hori M (1996) Cationic ring-opening polymerization of 3,6-di-O-benzyl-α-D-glucose 1,2,4-orthopivalate and the first chemical synthesis of cellulose. J Am Chem Soc 118(7):1677–1681. doi: https://doi.org/10.1021/ja953286u CrossRefGoogle Scholar
- Persson B, Nilsson S, Bergman R (1999) Dynamic surface tension of dilute aqueous solutions of nonionic cellulose derivatives in relation to other macromolecular characterization parameters. J Colloid Interface Sci 218(2):433–441. doi: https://doi.org/10.1006/jcis.1999.6449 CrossRefGoogle Scholar
- Segal L, Creely JJ, Martin AEJ, Conrad CM (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Text Res J 29(10):786–794. doi: https://doi.org/10.1177/004051755902901003 CrossRefGoogle Scholar
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