Abstract
In this paper, the influence of diamines on the intrinsic structure and molecular mobility of cellulosic complexes is discussed. Cellulose was pre-swollen by ethylenediamine then put in contact with a series of aliphatic diamines at a stoechiometric ratio. These materials were then characterized by Wide Angle X-Ray diffraction (WAXS) and solid-state \(^{13}C\) NMR spectroscopy. It was observed by WAXS that diamines are able to swell cellulose along the (010) crystallographic plane and are able to modify unit cell angle \(\gamma \) of cellulose monoclinic structure. Moreover according to their periodicity, ordered- or disordered-phases structures were identified in such cellulosic complexes by Cross Polarization - Magic Angle Spinning (CP-MAS) \(^{13}C\) NMR spectroscpy. Two-dimensional Wide-line Separation (2D WISE) and \(T_1\) relaxation time \(^{13}C\) NMR spectroscopy experiments showed that complexes do exhibit molecular motions between 23 and 90\(^{\circ }\)C. Modulated Differential Scanning Calorymetry (MDSC) further showed the presence of two glass transition temperatures \(T_g\), which were attributed, in combination with the \(^{13}C\) NMR spectroscopy observations through a multiscale approach, to relaxation motions internal to the diamines chemical structure and to the motion of cellulose–diamine planes respectively.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Date availability
Not applicable.
References
Badea E, Della Gatta G, D’Angelo D, Brunetti B, Rečková Z (2006) Odd-even effect in melting properties of 12 alkane-\(\alpha \), \(\omega \)-diamides. J Chem Thermodyn 38(12):1546–1552. https://doi.org/10.1016/j.jct.2006.04.004
Calahorra M, Cortazar M, Eguiazábal J, Guzmán G (1989) Thermogravimetric analysis of cellulose: effect of the molecular weight on thermal decomposition. J Appl Polym Sci 37(12):3305–3314. https://doi.org/10.1002/app.1989.070371203
Chanzy H (2011) The continuing debate over the structure of cellulose: historical perspective and outlook. Cellulose 18(4):853–856. https://doi.org/10.1007/s10570-011-9547-6
Chundawat SP, Bellesia G, Uppugundla N, da Costa Sousa L, Gao D, Cheh AM, Agarwal UP, Bianchetti CM, Phillips GN Jr, Langan P et al (2011) Restructuring the crystalline cellulose hydrogen bond network enhances its depolymerization rate. J Am Chem Soc 133(29):11163–11174. https://doi.org/10.1021/ja2011115
Creely J, Wade R (1975) Complexes of diamines with cellulose: Study of symmetrical and unsymmetrical terminal group effects. Text Res J 45(3):240–246. https://doi.org/10.1177/004051757504500309
Creely J, Wade R, French A (1978) X-ray diffraction, thermal, and physical studies of complexes of cellulose with secondary diamines. Text Res J 48(1):37–43. https://doi.org/10.1177/004051757804800106
Creely JJ, Segal L, Loeb L (1959) An x-ray study of new cellulose complexes with diamines containing three, five, six, seven, and eight carbon atoms. J Polym Sci 36(130):205–214. https://doi.org/10.1002/pol.1959.1203613017
Davis W, Barry A, Peterson F, King A (1943) X-ray studies of reactions of cellulose in non-aqueous systems. ii. interaction of cellulose and primary amines1. J Am Chem Soc 65(7):1294–1299. https://doi.org/10.1021/ja01247a012
Diddens I, Murphy B, Krisch M, Müller M (2008) Anisotropic elastic properties of cellulose measured using inelastic x-ray scattering. Macromolecules 41(24):9755–9759. https://doi.org/10.1021/ma801796u
Earl WL, VanderHart D (1981) Observations by high-resolution carbon-13 nuclear magnetic resonance of cellulose i related to morphology and crystal structure. Macromolecules 14(3):570–574. https://doi.org/10.1021/ma50004a023
Earl WL, VanderHart DL (1980) High resolution, magic angle sampling spinning carbon-13 nmr of solid cellulose i. J Am Chem Soc 102(9):3251–3252. https://doi.org/10.1021/ja00529a064
French AD (2017) Glucose, not cellobiose, is the repeating unit of cellulose and why that is important. Cellulose 24(11):4605–4609. https://doi.org/10.1007/s10570-017-1450-3
Gericke M, Trygg J, Fardim P (2013) Functional cellulose beads: preparation, characterization, and applications. Chem Rev 113(7):4812–4836. https://doi.org/10.1021/cr300242j
Gill S, Noll L (1972) Calorimetric study of association of diketopiperazine in water. J Phys Chem 76(21):3065–3068. https://doi.org/10.1021/j100665a027
Hallary JL, Lauprêtre F, Monnerie L (eds) (2010) Polymer Materials. Macroscopic Properties and Molecular Interpetrations. John Wiley & Sons, Hoboken
Heux L, Dinand E, Vignon M (1999) Structural aspects in ultrathin cellulose microfibrils followed by 13c cp-mas nmr. Carbohydr Polym 40(2):115–124. https://doi.org/10.1016/S0144-8617(99)00051-X
Hodgman C (ed) (1962) CRC Handbook of Chemistry and Physics, 44th edn. CRC Press, Cleveland
Hopmann RF (1974) Chemical relaxation as a mechanistic probe of hydrogen bonding. thermodynamics and kinetics of lactam isoassociation in nonpolar solvents. J Phys Chem 78(23):2341–2348. https://doi.org/10.1021/j150671a009
Ishikura Y (2011) Changes of wood properties treated with aqueous amine solution, bending tests and x-ray analysis of wood after amine treatment. J Mater Sci 46(11):3785–3791. https://doi.org/10.1007/s10853-011-5292-3
Jorgensen WL, Swenson CJ (1985) Optimized intermolecular potential functions for amides and peptides. hydration of amides. J Am Chem Soc 107(6):1489–1496. https://doi.org/10.1021/ja00292a007
Klotz IM, Franzen JS (1962) Hydrogen bonds between model peptide groups in solution. J Am Chem Soc 84(18):3461–3466. https://doi.org/10.1021/ja00877a009
Koham M (ed) (1995) Nylon Plastics Handbook. Carl Hanser Verlag, Munich
Kono H, Numata Y (2004) Two-dimensional spin-exchange solid-state nmr study of the crystal structure of cellulose ii. Polymer 45(13):4541–4547. https://doi.org/10.1016/j.polymer.2004.04.025
Kono H, Yunoki S, Shikano T, Fujiwara M, Erata T, Takai M (2002) Cp/mas 13c nmr study of cellulose and cellulose derivatives. 1. complete assignment of the cp/mas 13c nmr spectrum of the native cellulose. J Am Chem Soc 124(25):7506–7511. https://doi.org/10.1021/ja010704o
Larsson PT, Hult EL, Wickholm K, Pettersson E, Iversen T (1999) Cp/mas 13c-nmr spectroscopy applied to structure and interaction studies on cellulose i. Solid State Nucl Magn Reson 15(1):31–40. https://doi.org/10.1016/S0926-2040(99)00044-2
Larsson PT, Wickholm K, Iversen T (1997) A cp/mas13c nmr investigation of molecular ordering in celluloses. Carbohydr Res 302(1–2):19–25. https://doi.org/10.1016/S0008-6215(97)00130-4
Marčelja S (1974) Chain ordering in liquid crystals. i. even-odd effect. J Chem Phys 60(9):3599–3604. https://doi.org/10.1063/1.1681578
Mazeau K (2005) Structural micro-heterogeneities of crystalline i\(\beta \)-cellulose. Cellulose 12:339–349. https://doi.org/10.1007/s10570-005-2200-5
Mazeau K, Heux L (2003) Molecular dynamics simulations of bulk native crystalline and amorphous structures of cellulose. J Phys Chem B 107(10):2394–2403. https://doi.org/10.1021/jp0219395
Mizuno M, Hirai A, Matsuzawa H, Endo K, Suhara M, Kenmotsu M, Han CD (2002) Study of odd- even effect of flexible spacer length on the chain dynamics of main-chain thermotropic liquid-crystalline polymers using high-resolution solid-state 13c nuclear magnetic resonance spectroscopy. Macromolecules 35(7):2595–2601. https://doi.org/10.1021/ma011839h
Mori T, Chikayama E, Tsuboi Y, Ishida N, Shisa N, Noritake Y, Moriya S, Kikuchi J (2012) Exploring the conformational space of amorphous cellulose using nmr chemical shifts. Carbohydr Polym 90(3):1197–1203. https://doi.org/10.1016/j.carbpol.2012.06.027
Nishiyama Y (2009) Structure and properties of the cellulose microfibril. J Wood Sci 55(4):241–249. https://doi.org/10.1007/s10086-009-1029-1
Nishiyama Y, Johnson GP, French AD, Forsyth VT, Langan P (2008) Neutron crystallography, molecular dynamics, and quantum mechanics studies of the nature of hydrogen bonding in cellulose i\(\beta \). Biomacromolecules 9(11):3133–3140. https://doi.org/10.1021/bm800726v
Nishiyama Y, Langan P, Chanzy H (2002) Crystal structure and hydrogen-bonding system in cellulose i\(\beta \) from synchrotron x-ray and neutron fiber diffraction. J Am Chem Soc 124(31):9074–9082. https://doi.org/10.1021/ja0257319
Nishiyama Y, Sugiyama J, Chanzy H, Langan P (2003) Crystal structure and hydrogen bonding system in cellulose i\(\alpha \) from synchrotron x-ray and neutron fiber diffraction. J Am Chem Soc 125(47):14300–14306. https://doi.org/10.1021/ja037055w
Nishiyama Y, Wada M, Hanson BL, Langan P (2010) Time-resolved x-ray diffraction microprobe studies of the conversion of cellulose i to ethylenediamine-cellulose i. Cellulose 17:735–745. https://doi.org/10.1007/s10570-010-9415-9
Numata Y, Kono H, Kawano S, Erata T, Takai M (2003) Cross-polarization/magic-angle spinning 13c nuclear magnetic resonance study of cellulose i-ethylenediamine complex. J Biosci Bioeng 96(5):461–466. https://doi.org/10.1016/S1389-1723(03)70132-7
Pang Y, Jia D, Hu H, Hourston D, Song M (1999) A quantitative estimation of the extent of compatibilization in heterogeneous polymer blends using their heat capacity increment at the glass transition. J Appl Polym Sci 74(12):2868–2876
Parthasarathi R, Bellesia G, Chundawat S, Dale B, Langan P, Gnanakaran S (2011) Insights into hydrogen bonding and stacking interactions in cellulose. J Phys Chem A 115(49):14191–14202. https://doi.org/10.1021/jp203620x
Pinkert A, Marsh KN, Pang S, Staiger MP (2009) Ionic liquids and their interaction with cellulose. Chem Rev 109(12):6712–6728. https://doi.org/10.1021/cr9001947
Puiggalí J, Franco L, Alemán C, Subirana J (1998) Crystal structures of nylon 5, 6. a model with two hydrogen bond directions for nylons derived from odd diamines. Macromolecules 31(24):8540–8548. https://doi.org/10.1021/ma971895b
Reddy MM, Vivekanandhan S, Misra M, Bhatia SK, Mohanty AK (2013) Biobased plastics and bionanocomposites: Current status and future opportunities. Progr Polym Sci 38(10–11):1653–1689. https://doi.org/10.1016/j.progpolymsci.2013.05.006
Rios de Anda A, Fillot LA, Long DR, Sotta P (2016) Influence of the amorphous phase molecular mobility on impact and tensile properties of polyamide 6, 6. J Appl Polym Sci 133(21). https://doi.org/10.1002/app.43457
Rios de Anda A, Fillot LA, Preda F, Rossi S, Long D, Sotta P (2014) Sorption and plasticization effects of ethanol-toluene-isooctane ternary mixtures in polyamide 6, 6 and induced plasticization effects. Eur Polym J 55:199–209. https://doi.org/10.1016/j.eurpolymj.2014.04.001
Rios de Anda A, Fillot LA, Rossi S, Long D, Sotta P (2011) Influence of the sorption of polar and non-polar solvents on the glass transition temperature of polyamide 6, 6 amorphous phase. Polym Eng Sci 51(11):2129–2135. https://doi.org/10.1002/pen.22064
Schmidt-Rohr K, Spiess HW (eds) (2005) Multidimensional Solid-State NMR and Polymers. Academic Press, London
Schroeter J, Felix F (2005) Melting cellulose. Cellulose 12:159–165. https://doi.org/10.1007/s10570-004-0344-3
Segal L (1964) Comparison of the effects of allylamine and n-propylamine on cellulose. J Polym Sci Part A Gener Papers 2(6):2951–2961. https://doi.org/10.1002/pol.1964.100020643
Segal L, Eggerton F (1964) Study of the hexamethylenediamine-cellulose complex. J Polym Sci Part A Gener Papers 2(11):4845–4863. https://doi.org/10.1002/pol.1964.100021115
Segal L, Loeb L (1960) The diethylenetriamine-cellulose complex. J Polym Sci 42(140):351–356. https://doi.org/10.1002/pol.1960.1204214006
Sewda K, Maiti S (2013) Dynamic mechanical properties of high density polyethylene and teak wood flour composites. Polym Bull 70:2657–2674. https://doi.org/10.1007/s00289-013-0941-0
Su X, Kimura S, Wada M, Kuga S (2011) Stoichiometry and stability of cellulose-hydrazine complexes. Cellulose 18:531–537. https://doi.org/10.1007/s10570-011-9505-3
Thalladi VR, Boese R, Weiss HC (2000) The melting point alternation in alpha, omega-alkanediols and alpha, omega-alkanediamines: Interplay between hydrogen bonding and hydrophobic interactions the melting point alternation in n-alkanes and derivatives part 2. Angewandte Chemie 39(5):918–922
Uno K, Ogawa Y, Nakamura N (2008) Polymorphism of long-chain alkane-\(\alpha \), \(\omega \)-diols with an even number of carbon atoms. Cryst Growth Des 8(2):592–599. https://doi.org/10.1021/cg700729q
VanderHart DL, Atalla R (1984) Studies of microstructure in native celluloses using solid-state carbon-13 nmr. Macromolecules 17(8):1465–1472. https://doi.org/10.1021/ma00138a009
Wada M, Heux L, Nishiyama Y, Langan P (2009) The structure of the complex of cellulose i with ethylenediamine by x-ray crystallography and cross-polarization/magic angle spinning 13 c nuclear magnetic resonance. Cellulose 16:943–957. https://doi.org/10.1007/s10570-009-9338-5
Wada M, Kwon GJ, Nishiyama Y (2008) Structure and thermal behavior of a cellulose i- ethylenediamine complex. Biomacromolecules 9(10):2898–2904. https://doi.org/10.1021/bm8006709
Wada M, Nishiyama Y, Bellesia G, Forsyth T, Gnanakaran S, Langan P (2011) Neutron crystallographic and molecular dynamics studies of the structure of ammonia-cellulose i: rearrangement of hydrogen bonding during the treatment of cellulose with ammonia. Cellulose 18:191–206. https://doi.org/10.1007/s10570-010-9488-5
Wada M, Okano T, Sugiyama J (2001) Allomorphs of native crystalline cellulose i evaluated by two equatoriald-spacings. J Wood Sci 47(2):124–128. https://doi.org/10.1007/BF00780560
Wang H, Gurau G, Rogers RD (2012a) Ionic liquid processing of cellulose. Chem Soc Rev 41(4):1519–1537. https://doi.org/10.1039/C2CS15311D
Wang Z, Liu S, Matsumoto Y, Kuga S (2012b) Cellulose gel and aerogel from licl/dmso solution. Cellulose 19:393–399. https://doi.org/10.1007/s10570-012-9651-2
Wickholm K, Larsson PT, Iversen T (1998) Assignment of non-crystalline forms in cellulose i by cp/mas 13c nmr spectroscopy. Carbohydr Res 312(3):123–129. https://doi.org/10.1016/S0008-6215(98)00236-5
Wormald P, Wickholm K, Larsson PT, Iversen T (1996) Conversions between ordered and disordered cellulose. effects of mechanical treatment followed by cyclic wetting and drying. Cellulose 3:141–152. https://doi.org/10.1007/BF02228797
Wu J, Bai J, Xue Z, Liao Y, Zhou X, Xie X (2015) Insight into glass transition of cellulose based on direct thermal processing after plasticization by ionic liquid. Cellulose 22:89–99. https://doi.org/10.1007/s10570-014-0502-1
Acknowledgements
Not applicable.
Funding
This work was funded by, and author A. Ríos de Anda received research support from Solvay.
Author information
Authors and Affiliations
Contributions
ARA and AE conducted the experiments, YN, KM, CV and LH supervised the project. All authors contributed to the writing and editing of the manuscript.
Corresponding author
Ethics declarations
Conflict of interest
Not applicable.
Ethical approval and consent to participate
Not applicable.
Consent for publication
All authors have given consent for publication.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
This article is part of a collection of articles in honor of Dr. Henri Chanzy on the occasion of his 90th birthday. The article was not finished in time to be bound with the rest of the papers in the Special Issue #13, September, 2023
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
de Anda, A.R., Ettori, A., Nishiyama, Y. et al. Influence on the structure and the molecular mobility of cellulose–diamine complexes studied by a multiscale experimental approach. Cellulose 31, 2713–2727 (2024). https://doi.org/10.1007/s10570-024-05786-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-024-05786-z