Elsevier

Carbohydrate Polymers

Volume 111, 13 October 2014, Pages 280-287
Carbohydrate Polymers

Photoresponsive cellulose fibers by surface modification with multifunctional cellulose derivatives

https://doi.org/10.1016/j.carbpol.2014.04.089Get rights and content

Highlights

  • Surface modification of pulp fibers with multifunctional cellulose derivatives.

  • Evaluation of the mechanism of adsorption by SPR.

  • Surface characterization by means of ToF-SIMS.

  • Preparation of photoactive fibers.

Abstract

Eucalyptus bleached kraft pulp fibers were modified by adsorption of novel bio-based multifunctional cellulose derivatives in order to generate light responsive surfaces. The cellulose derivatives used were decorated with both cationic groups (degree of substitution, DS of 0.34) and photoactive groups (DS of 0.11 and 0.37). The adsorption was studied by UV–vis spectroscopy, surface plasmon resonance (SPR) and time-of-flight secondary ion mass spectroscopy (ToF-SIMS). The adsorption isotherms followed the Freundlich model and it turned out that the main driving force for the adsorption was electrostatic interaction. Moreover, strong indications for hydrophobic interactions between the fibers and the derivatives and the derivatives themselves were found. ToF-SIMS imaging revealed an even distribution of the derivatives on the fiber surfaces. The modified fibers underwent fast photocrosslinking under UV-irradiation as demonstrated by light absorbance and fluorescence measurements. Thus, our results proved that the modified fibers exhibited light-responsive properties and can potentially be used for the manufacture of smart bio-based materials.

Introduction

Pulp fibers are intermediate products mainly used in the production of paper and paper boards (Freire, Silvestre, Gandini, & Neto, 2011). However, pulp fibers represent also an attractive substrate for the manufacturing of novel materials owing to their outstanding characteristics. They are relatively cheap, renewable, biodegradable, and can be recycled or converted to energy by combustion at the end of the life cycle of the product. Additionally, the fibers have good mechanical properties and relatively low density (Belgacem and Gandini, 2008, Freire et al., 2011, Ly et al., 2010).

Currently more than 180 million ton per year of pulp fibers (Sixta, 2006) are produced by well-established technologies like mechanical, chemo-mechanical and chemical pulping methods. The properties and the chemical composition (bulk and surface) of pulp fibers from the classical pulping techniques are very well-studied and vary significantly depending on the raw material and the way of the manufacturing. In order to utilize pulp fibers in new value added products, current research is focusing on the modification of their surfaces while keeping bulk properties such as morphology and native fiber wall structure (Grönqvist et al., 2006, Hedenberg and Gatenholm, 1995, Pan and Ragauskas, 2012). Biological (e.g. by enzymes, fungi), chemical (carboxylation, grafting) or plasma treatments and adsorption methods can be applied for this purpose (Gandini and Pasquini, 2012, Utsel, 2012).

From our point of view, the adsorption method appears to be the most promising tool among the techniques mentioned since it is water-based and can be easily combined with existing fiber line stages (Muguet, Pedrazzi, & Colodette, 2011). Traditionally, the research in fiber chemistry and technology has been mainly focusing on the improvement of mechanical, drainage and optical properties of pulp by adsorbing polysaccharides and polysaccharide-based polyelectrolytes for paper manufacture (Köhnke et al., 2010, Schönberg et al., 2001). In this regard, the application of underutilized biomass derived polysaccharides like hemicelluloses recently came into focus (Schwikal et al., 2011, Silva et al., 2011, Vega et al., 2012).

Functional biopolymers with stimuli-responsive capabilities can be used for the modification of pulp in order to generate new fiber-based materials, whose properties could be triggered by an external stimulus. Multifunctional polysaccharide derivatives decorated with cationic and, in particular, light responsive substituents can be applied for this purpose. The light induced alterations, including isomerization, dissociation or crosslinking, of the photoactive substituents were described to cause changes in physical properties of the polymers itself or polymeric solutions (Irie, 1990, Wondraczek et al., 2010, Wondraczek et al., 2011). Consequently, the possibility to control the properties of the interface of the fibers to which they are attached can be expected, and the properties of fiber-based materials and composites might be influenced.

The focus of the studies presented in this paper was to gain information about the interaction of pulp fibers and cellulose derivatives, which were decorated on one hand with cationic (3-carboxypropyl)trimethylammonium chloride ester moieties and on the other with hydrophobic (photoactive) 2-[(4-methyl-2-oxo-2H-chromen-7-yl)oxy]acetate substituents (Wondraczek, Pfeifer, & Heinze, 2012). In particular, the influence of the hydrophobic/hydrophilic balance of the derivatives on the adsorption behavior was investigated and a tentative hypothesis of the interaction of pulp fibers and such multifunctional cellulose derivatives was suggested. Moreover, the fiber surface composition and lateral distribution was evaluated by means of ToF-SIMS spectrometry and imaging.

Section snippets

Materials

Eucalyptus air-dried unrefined bleached kraft pulp (bleaching sequence: A-ZD-EOP-D-Z-P brightness: 86% ISO) obtained from Botnia (Kaskö) was disintegrated according ISO 5263:1995(E). The disintegrated pulp was dewatered by centrifugation and the dry matter content according to ISO 638-1978 was determined to be approximately 30%. The total amount of anionic groups in the pulp was determined by the methylene blue sorption method (Fardim, Moreno, & Holmbom, 2005) to be 99 μmol/g. The amount of

Interaction of PCCDs with the pulp fibers

Multifunctional cellulose-based polyelectrolytes decorated with photoactive 2-[(4-methyl-2-oxo-2H-chromen-7-yl)oxy]acetate and cationic (3-carboxypropyl)trimethylammonium chloride ester moieties were applied for the modification of eucalyptus unrefined bleached kraft pulp (Fig. 1). The different photoactive cationic cellulose derivatives (PCCDs) possess a degree of substitution of cationic groups (DSN+) of 0.34 and photoactive groups (DSPhoto) of 0.11 (PCCD-1) and 0.37 (PCCD-2), respectively.

Conclusions

Novel multifunctional cellulose derivatives decorated with both cationic and photoactive moieties were adsorbed onto the pulp fiber surfaces. Based on the results from UV–vis spectroscopy and SPR measurements, it was found that the electrostatic interaction was the main driving force of the adsorption of the derivatives onto the fibers. However, hydrophobic interactions between the fibers and the cellulose derivatives as well as between the cellulose derivatives themselves also contributed to

Acknowledgements

Finnish Funding Agency for Technology and Innovation (Tekes) is acknowledged for funding. The authors are grateful to Professor Peter Mattjus from Åbo Akademi University for the access to the SPR instrument and to Josefin Halin for her assistance with the SPR measurements. Annett Pfeifer and Cíntia Salomão Pinto Zarth are acknowledged for providing PCCDs and CCDs.

References (29)

  • C.S.R. Freire et al.

    New materials from cellulose fibers. A contribution to the implementation of the integrated biorefinery concept

    O PAPEL

    (2011)
  • S. Grönqvist et al.

    Laccase-catalysed functionalisation of TMP with tyramine

    Holzforschung

    (2006)
  • P. Hedenberg et al.

    Conversion of plastic/cellulose waste into composites. I. Model of the interphase

    Journal of Applied Polymer Science

    (1995)
  • M. Irie

    Properties and applications of photoresponsive polymers

    Pure and Applied Chemistry

    (1990)
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