Hydroxypropyl cellulose (HPC)-esters were prepared by a homogeneous reaction of HPC with fatty acid chlorides. The effects of different solvent systems and reaction additives were evaluated, and plain, dried THF was established as best system in terms of toxicity, targeted synthesis of desired degree of substitution (DS), chain degradation and ease of workup. Moreover, pyridine/4-dimethylaminopyridine (4-DMAP) was found to be the fastest system overall. The reaction kinetics with different fatty acids—lauric, myristic, palmitic and stearic acid—were characterized and comprehensively compared. The DS could be adjusted precisely, giving control over the glass transition temperature (Tg)/melting point (Tm) of the HPC-esters, yielding a toolbox to tailor HPC-ester. In a next step, nanoparticles are formed from HPC stearic acid ester and used to generate superhydrophobic surface coatings, thereby demonstrating one of the interesting potential uses of this sustainable material.
This is a preview of subscription content, log in to check access.
Buy single article
Instant access to the full article PDF.
Price includes VAT for USA
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
This is the net price. Taxes to be calculated in checkout.
Chen WW, Weng WG, Fu M (2017) Hydroxypropyl cellulose-based esters for thermal energy storage by grafting with palmitic-stearic binary acids. J Appl Polym Sci 134:44949
Daruwalla EH, Nabar GM (1956) Acid hydrolysis of cellulose. J Polym Sci 20:205–208
Geissler A (2017) Charakterisierung und Applikation von Fettsäureestern der Cellulose und deren kolloidaler Systeme vol 10. Makromolekulare Chemie, 1. Auflage edn., Aachen
Geissler A, Chen L, Zhang K, Bonaccurso E, Biesalski M (2013) Superhydrophobic surfaces fabricated from nano- and microstructured cellulose stearoyl esters. Chem Commun (Camb) 49:4962–4964
Heinze T, Glasser WG (1998) The role of novel solvents and solution complexes for the preparation of highly engineered cellulose derivatives. Cellul Deriv Am Chem Soc 688:2–18
Heinze T, Koschella A (2005) Solvents applied in the field of cellulose chemistry: a mini review. Polímeros 15:84–90
Ho FFL, Ward GA, Kohler RR (1972) Determination of molar substitution and degree of substitution of hydroxypropyl cellulose by nuclear magnetic-resonance spectrometry. Anal Chem 44:178–181
Hou HQ, Reuning A, Wendorff JH, Greiner A (2000) Tuning of the pitch height of thermotropic cellulose esters. Macromol Chem Phys 201:2050–2054
Hou HQ, Reuning A, Wendorff JH, Greiner A (2001) Effect of blending of cholesteric cellulose esters on the pitch height. Macromol Biosci 1:45–48
Huang B, Ge JJ, Li YH, Hou HQ (2007) Aliphatic acid esters of (2-hydroxypropyl) cellulose—effect of side chain length on properties of cholesteric liquid crystals. Polymer 48:264–269
Hubbard P, Brittain WJ (1998) Mechanism of amine-catalyzed ester formation from an acid chloride and alcohol. J Org Chem 63:677–683
Ishizaki T, Uenuma S, Furumi S (2015) Thermotropic properties of cholesteric liquid crystal from hydroxypropyl cellulose mixed esters. Kobunshi Ronbunshu 72:737–745
Khan FZ, Shiotsuki M, Sanda F, Nishio Y, Masuda T (2008) Synthesis and properties of amino acid esters of hydroxypropyl cellulose. J Polym Sci Pol Chem 46:2326–2334
Launer HF, Wilson WK (1950) Preparing cuprammonium solvent and cellulose solutions. Anal Chem 22:455–458
Lee JL, Pearce EM, Kwei TK (1997) Side-chain crystallization in alkyl-substituted semiflexible polymers. Macromolecules 30:6877–6883
Levin D (1997) Potential toxicological concerns associated with carboxylic acid chlorination and other reactions. Org Process Res Dev 1:182
Liu YJ, Lotero E, Goodwin JG (2006) Effect of carbon chain length on esterification of carboxylic acids with methanol using acid catalysis. J Catal 243:221–228
Malm CJ, Tanghe LJ (1955) Chemical reactions in the making of cellulose acetate. Ind Eng Chem 47:995–999
Malm CJ, Barkey KT, Schmitt JT, May DC (1957) Evaluating cellulose acetylation reactivity. Ind Eng Chem 49:763–767
Meller A (1953) Studies on modified cellulose. 3. Characterization of the reactivity and supermolecular structure cellulose fibers. Tappi 36:264–267
Ostlund A, Lundberg D, Nordstierna L, Holmberg K, Nyden M (2009) Dissolution and gelation of cellulose in TBAF/DMSO solutions: the roles of fluoride ions and water. Biomacromol 10:2401–2407
Philipp B (1993) Organic-solvents for cellulose as a biodegradable polymer and their applicability for cellulose spinning and derivatization. J Macromol Sci Pure A30:703–714
Richardson S, Andersson T, Brinkmalm G, Wittgren B (2003) Analytical approaches to improved characterization of substitution in hydroxypropyl cellulose. Anal Chem 75:6077–6083
Sealey JE, Samaranayake G, Todd JG, Glasser WG (1996) Novel cellulose derivatives. 4. Preparation and thermal analysis of waxy esters of cellulose. J Polym Sci Pol Phys 34:1613–1620
Sereti V, Stamatis H, Pappas C, Polissiou M, Kolisis FN (2001) Enzymatic acylation of hydroxypropyl cellulose in organic media and determination of ester formation by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. Biotechnol Bioeng 72:495–500
Sihtola H, Kaila E, Laamanen L (1957) Cupriethylenediamine and cuprammonium hydroxide as solvents in molecular fractionation of cellulose. J Polym Sci 23:809–824
Situ FM et al (2015) Cellulose-based polymeric liquid crystals as a biomimetic modifier for suppressing protein adsorption. J Wuhan Univ Technol 30:416–422
Steinmeier H, Zugenmaier P (1988) Formation of liquid-crystalline phases by two phenyl-alkanoyl esters of O-(hydroxypropyl)cellulose and the (3-chlorophenyl)urethane of cellulose. Carbohyd Res 173:75–88
Tseng SL, Laivins GV, Gray DG (1982) Propanoate ester of (2-hydroxypropyl)cellulose—a thermotropic cholesteric polymer that reflects visible-light at ambient-temperatures. Macromolecules 15:1262–1264
Tu M, Han WQ, Zeng R, Best SM, Cameron RE (2012) A study of surface morphology and phase separation of polymer/cellulose liquid crystal composite membranes. Colloid Surface A 407:126–132
Wüstenberg T (2014) Hydroxypropylcellulose. In: Cellulose and cellulose derivatives in the food industry. Wiley, New York, pp 319–342
Yamagishi TA, Guittard F, Godinho MH, Martins AF, Cambon A, Sixou P (1994) Comparison of thermal and cholesteric mesophase properties among the 3 kind of hydroxypropylcellulose (Hpc). Deriv Polym Bull 32:47–54
Zhang ZG, Li GN, Hu GL, Sun YY (2013) Theoretical research on the mechanism of the dimerization reactions of alkyl ketene. J Chem 2013:481586
The authors would like to thank Martina Ewald and Heike Herbert for technical support and GPC measurements. Furthermore, we would like to thank Christian Rüttiger for conducting DSC measurements, and we would like to thank Dr. A. Geissler for valuable scientific discussions. This work was funded in part by the DFG Collaborative Research Center 1194 (SFB1194 “Wechelseitige Beeinflussung von Transport- und Benetzungsvorgängen”).
Conflict of interest
The authors declare no conflict of interest.
Electronic supplementary material
Below is the link to the electronic supplementary material.
About this article
Cite this article
Nau, M., Seelinger, D. & Biesalski, M. Functional surface coatings from tailor-made long-chain hydroxypropyl cellulose ester nanoparticles. Cellulose 25, 5769–5780 (2018). https://doi.org/10.1007/s10570-018-1981-2
- Hydroxypropyl cellulose
- Sustainable thermoplastics
- Bio based polymer
- Kinetic investigation
- Surface coating