Abstract
Due to the fact that natural cellulose cannot be melted, it is still challenging to process this biopolymer via thermoplastic processing methods. Herein, polycaprolactone diol was grafted onto regenerated cellulose (RC) via hydroxyl/isocyanate chemistry in dimethyl sulfoxide to endow cellulose with thermoplasticity. By adjusting the reaction parameters including the feeding ratios of reactants and reaction time, several homogeneous cellulose grafted polyurethanes (RC-g-PU) with the degree of substitution (DS) ranging from 0.49 to 1.48 and degree of polymerization ranging from 1.84 to 3.3 were synthesized. The thermoplasticity of the obtained RC-g-PU was well characterized by differential scanning calorimetry and optical microscope. The results revealed that the prepared RC-g-PU with DS values ranging from 1.01 to 1.48 can be melted at above 168.4 °C because PU side chains can serve as internal plasticizers and prevent the restacking of cellulose chains. Eventually, the synthesized thermoplastic RC-g-PU can be processed into transparent films by hot-pressing at 170 °C. Therefore, this research constructs a melt-processable cellulose derivative by a simple and engineering method.
This is a preview of subscription content, log in via an institution to check access.
Photo credit: logotype of Sichuan University, permission granted
Similar content being viewed by others
References
Abushammala H (2019) On the para/ortho reactivity of isocyanate groups during the carbamation of cellulose nanocrystals using 2,4-toluene diisocyanate. Polymers 11:1164. https://doi.org/10.3390/polym11071164
Abushammala H, Mao J (2019) A review of the surface modification of cellulose and nanocellulose using aliphatic and aromatic mono- and di-isocyanates. Molecules 24:2782. https://doi.org/10.3390/molecules24152782
Bondeson D, Syre P, Niska KO (2007) All cellulose nanocomposites produced by extrusion. J Biobased Mater Bioenergy 1:367–371. https://doi.org/10.1166/jbmb.2007.011
Cao X, Habibi Y, Lucia LA (2009) One-pot polymerization, surface grafting, and processing of waterborne polyurethane–cellulose nanocrystal nanocomposites. J Mater Chem 19:7137–7145. https://doi.org/10.1039/b910517d
Chen H et al (2018a) Efficient transesterification reaction of cellulose with vinyl esters in DBU/DMSO/CO2 solvent system at low temperature. Cellulose 25:6935–6945. https://doi.org/10.1007/s10570-018-2078-7
Chen Z, Zhang J, Xiao P, Tian W, Zhang J (2018b) Novel thermoplastic cellulose esters containing bulky moieties and soft segments. ACS Sustain Chem Eng 6:4931–4939. https://doi.org/10.1021/acssuschemeng.7b04466
Chien YC, Chuang WT, Jeng US, Hsu SH (2017) Preparation, characterization, and mechanism for biodegradable and biocompatible polyurethane shape memory elastomers. ACS Appl Mater Interfaces 9:5419–5429. https://doi.org/10.1021/acsami.6b11993
Cielecka I, Szustak M, Kalinowska H, Gendaszewska-Darmach E, Ryngajłło M, Maniukiewicz W, Bielecki S (2019) Glycerol-plasticized bacterial nanocellulose-based composites with enhanced flexibility and liquid sorption capacity. Cellulose 26:5409–5426. https://doi.org/10.1007/s10570-019-02501-1
Druel L, Niemeyer P, Milow B, Budtova T (2018) Rheology of cellulose-[DBNH][CO2Et] solutions and shaping into aerogel beads. Green Chem 20:3993–4002. https://doi.org/10.1039/c8gc01189c
French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896. https://doi.org/10.1007/s10570-013-0030-4
Hanabusa H, Izgorodina EI, Suzuki S, Takeoka Y, Rikukawa M, Yoshizawa-Fujita M (2018) Cellulose-dissolving protic ionic liquids as low cost catalysts for direct transesterification reactions of cellulose. Green Chem 20:1412–1422. https://doi.org/10.1039/c7gc03603e
Isogai A, Atalla RH (1998) Dissolution of cellulose in aqueous NaOH solutions. Cellulose 5:309–319. https://doi.org/10.1023/A:1009272632367
Jarvis M (2003) Cellulose stacks up. Nature 426:611. https://doi.org/10.1038/426611a
Jia R, Tian W, Bai H, Zhang J, Wang S, Zhang J (2019) Amine-responsive cellulose-based ratiometric fluorescent materials for real-time and visual detection of shrimp and crab freshness. Nat Commun 10:795. https://doi.org/10.1038/s41467-019-08675-3
Klemm D, Heublein B, Fink HP, Bohn A (2005) Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem Int Ed 44:3358–3393. https://doi.org/10.1002/anie.200460587
Kontturi E, Laaksonen P, Linder MB, Nonappa Groschel AH, Rojas OJ, Ikkala O (2018) Advanced materials through assembly of nanocelluloses. Adv Mater 30:e1703779. https://doi.org/10.1002/adma.201703779
Kostag M, Gericke M, Heinze T, El Seoud OA (2019) Twenty-five years of cellulose chemistry: innovations in the dissolution of the biopolymer and its transformation into esters and ethers. Cellulose 26:139–184. https://doi.org/10.1007/s10570-018-2198-0
Kuga S, Wu M (2019) Mechanochemistry of cellulose. Cellulose 26:215–225. https://doi.org/10.1007/s10570-018-2197-1
Laurichesse S, Huillet C, Avérous L (2014) Original polyols based on organosolv lignin and fatty acids: new bio-based building blocks for segmented polyurethane synthesis. Green Chem 16:3958–3970. https://doi.org/10.1039/C4GC00596A
Li WY, Jin AX, Liu CF, Sun RC, Zhang AP, Kennedy JF (2009) Homogeneous modification of cellulose with succinic anhydride in ionic liquid using 4-dimethylaminopyridine as a catalyst. Carbohydr Polym 78:389–395. https://doi.org/10.1016/j.carbpol.2009.04.028
Ling Z et al (2019) Effects of ball milling on the structure of cotton cellulose. Cellulose 26:305–328. https://doi.org/10.1007/s10570-018-02230-x
Luan Y, Wu J, Zhan M, Zhang J, Zhang J, He J (2013) “One pot” homogeneous synthesis of thermoplastic cellulose acetate-graft-poly(l-lactide) copolymers from unmodified cellulose. Cellulose 20:327–337. https://doi.org/10.1007/s10570-012-9818-x
Medronho B, Lindman B (2015) Brief overview on cellulose dissolution/regeneration interactions and mechanisms. Adv Colloid Interface Sci 222:502–508. https://doi.org/10.1016/j.cis.2014.05.004
Onwukamike KN, Tassaing T, Grelier S, Grau E, Cramail H, Meier MAR (2017) Detailed understanding of the DBU/CO2 switchable solvent system for cellulose solubilization and derivatization. ACS Sustain Chem Eng 6:1496–1503. https://doi.org/10.1021/acssuschemeng.7b04053
Onwukamike KN, Grelier S, Grau E, Cramail H, Meier MAR (2018) Sustainable transesterification of cellulose with high oleic sunflower oil in a DBU–CO2 switchable solvent. ACS Sustain Chem Eng 6:8826–8835. https://doi.org/10.1021/acssuschemeng.8b01186
Onwukamike KN, Grelier S, Grau E, Cramail H, Meier MAR (2019a) Critical review on sustainable homogeneous cellulose modification: why renewability is not enough. ACS Sustain Chem Eng 7:1826–1840. https://doi.org/10.1021/acssuschemeng.8b04990
Onwukamike KN, Lapuyade L, Maillé L, Grelier S, Grau E, Cramail H, Meier MAR (2019b) Sustainable approach for cellulose aerogel preparation from the DBU–CO2 switchable solvent. ACS Sustain Chem Eng 7:3329–3338. https://doi.org/10.1021/acssuschemeng.8b05427
Pena CA, Soto A, King AWT, Rodríguez H (2019) Improved reactivity of cellulose via its crystallinity reduction by nondissolving pretreatment with an ionic liquid. ACS Sustain Chem Eng 7:9164–9171. https://doi.org/10.1021/acssuschemeng.8b06357
Petridis L, Smith JC (2018) Molecular-level driving forces in lignocellulosic biomass deconstruction for bioenergy. Nat Rev Chem 2:382–389. https://doi.org/10.1038/s41570-018-0050-6
Piras CC, Fernández-Prieto S, De Borggraeve WM (2019) Ball milling: a green technology for the preparation and functionalisation of nanocellulose derivatives. Nanoscale Adv 1:937–947. https://doi.org/10.1039/c8na00238j
Reyes G, Borghei M, King AWT, Lahti J, Rojas OJ (2019) Solvent welding and imprinting cellulose nanofiber films using ionic liquids. Biomacromol 20:502–514. https://doi.org/10.1021/acs.biomac.8b01554
Rol F, Belgacem MN, Gandini A, Bras J (2019) Recent advances in surface-modified cellulose nanofibrils. Prog Polym Sci 88:241–264. https://doi.org/10.1016/j.progpolymsci.2018.09.002
Schroeter J, Felix F (2005) Melting cellulose. Cellulose 12:159–165. https://doi.org/10.1007/s10570-004-0344-3
Sirviö JA (2019) Fabrication of regenerated cellulose nanoparticles by mechanical disintegration of cellulose after dissolution and regeneration from a deep eutectic solvent. J Mater Chem A 7:755–763. https://doi.org/10.1039/c8ta09959f
Song L, Yang Y, Xie H, Liu E (2015) Cellulose dissolution and in situ grafting in a reversible system using an organocatalyst and carbon dioxide. Chemsuschem 8:3217–3221. https://doi.org/10.1002/cssc.201500378
Söyler Z, Meier MAR (2017) Sustainable functionalization of cellulose and starch with diallyl carbonate in ionic liquids. Green Chem 19:3899–3907. https://doi.org/10.1039/c7gc01978e
Söyler Z, Onwukamike KN, Grelier S, Grau E, Cramail H, Meier MAR (2018) Sustainable succinylation of cellulose in a CO2-based switchable solvent and subsequent Passerini 3-CR and Ugi 4-CR modification. Green Chem 20:214–224. https://doi.org/10.1039/c7gc02577g
Tabaght FE et al (2020) Cellulose grafted aliphatic polyesters: synthesis, characterization and biodegradation under controlled conditions in a laboratory test system. J Mol Struct 1205:127582. https://doi.org/10.1016/j.molstruc.2019.127582
Tanaka S, Iwata T, Iji M (2017) Long/short chain mixed cellulose esters: effects of long acyl chain structures on mechanical and thermal properties. ACS Sustain Chem Eng 5:1485–1493. https://doi.org/10.1021/acssuschemeng.6b02066
Wang S, Lu A, Zhang L (2016) Recent advances in regenerated cellulose materials. Prog Polym Sci 53:169–206. https://doi.org/10.1016/j.progpolymsci.2015.07.003
Wu J, Bai J, Xue Z, Liao Y, Zhou X, Xie X (2014) 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
Xu Q et al (2017) Organocatalytic cellulose dissolution and in situ grafting of ε-caprolactone via ROP in a reversible DBU/DMSO/CO2 system. ChemistrySelect 2:7128–7134. https://doi.org/10.1002/slct.201701639
Yan C, Zhang J, Lv Y, Yu J, Wu J, Zhang J, He J (2009) Thermoplastic cellulose-graft-poly(l-lactide) copolymers homogeneously synthesized in an ionic liquid with 4-dimethylaminopyridine catalyst. Biomacromol 10:2013–2018. https://doi.org/10.1021/bm900447u
Yang Y, Xie H, Liu E (2014) Acylation of cellulose in reversible ionic liquids. Green Chem 16:3018–3023. https://doi.org/10.1039/c4gc00199k
Yao X, Qi X, He Y, Tan D, Chen F, Fu Q (2014) Simultaneous reinforcing and toughening of polyurethane via grafting on the surface of microfibrillated cellulose. ACS Appl Mater Interfaces 6:2497–2507. https://doi.org/10.1021/am4056694
Yi H et al (2019) Ultra-adaptable and wearable photonic skin based on a shape-memory, responsive cellulose derivative. Adv Funct Mater 29:1902720. https://doi.org/10.1002/adfm.201902720
Zhang X, Wu X, Gao D, Xia K (2012) Bulk cellulose plastic materials from processing cellulose powder using back pressure-equal channel angular pressing. Carbohydr Polym 87:2470–2476. https://doi.org/10.1016/j.carbpol.2011.11.019
Zhao Y, Moser C, Henriksson G (2018) Transparent composites made from tunicate cellulose membranes and environmentally friendly polyester. Chemsuschem 11:1728–1735. https://doi.org/10.1002/cssc.201800627
Acknowledgments
The authors acknowledge the financial support from the National Natural Science Foundation of China (Grants: 51873128 and 51721091).
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Hou, DF., Tan, H., Li, ML. et al. Synthesis of thermoplastic cellulose grafted polyurethane from regenerated cellulose. Cellulose 27, 8667–8679 (2020). https://doi.org/10.1007/s10570-020-03389-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-020-03389-y