Regenerated bacterial cellulose fibres.

The global shortage of cotton for textile production, forces the exploitation of forests´ lignocellulosic biomass to produce man-made cellulosic fibres (MMCF). This has a considerable environmental impact, pressing the textile industry to search for new sustainable materials and to the development of sustainable recycling processes. Bacterial cellulose (BC), an exopolysaccharide produced by fermentation, could represent such an alternative. In particular, we tested the possibility of improving the mechanical properties of cellulose filaments with a low degree of polymerization (DP) by combining them with high DP from BC, so far exploited to little extent in the textile field. In this work, BC with different degrees of polymerization (DPcuaxam) (BCneat: 927; BCdep:634 and BCblend: 814) were dissolved in N-methylmorpholine-N-oxide (NMMO) and their spinnability was studied. The rheological behaviour of the dopes was assessed and all were found to be spinnable, at suitable concentrations (BCneat:9.0 %; BCdep:12.2 %; BCblend:10.5 %). A continuous spinning was obtained and the resulting filaments offered similar mechanical performance to those of Lyocell. Further, the blending of BC pulps with different DPs (BCblend, obtained by combining BCneat and BCdep) allowed the production of fibres with higher stiffness (breaking tenacity 56.4 CN.tex-1) and lower elongation (8.29 %), as compared to samples with more homogeneous size distribution (neat BC and depolymerized BC).

Effects of cationic xylan from annual plants on the mechanical properties of paper.

Xylan from oat spelt and wheat was used as an additive to enhance the dry strength of paper. The absorption of xylan by the cellulose fibers was increased by cationization to different degrees of substitution. Paper hand sheets with different doses of xylan and industrial cationic starch were produced, and the mechanical properties were determined. Absorption measurements of cationic oat spelt xylan on pulp fibers explained the differing influences of low and high cationized xylan addition on paper strength. The addition of cationic oat spelt xylan with a degree of substitution of 0.1 at a 4% dose provided the largest improvement in the tensile-index (67%), burst-index (105%) and tear-index (77%). Compared to cationic starch, cationic oat spelt xylan additives led to similar paper strength values, excepting the tear strength. The structural differences and protein impurities made the wheat xylan unsuitable as a strength additive for paper pulp.

Studies on the tosylation of cellulose in mixtures of ionic liquids and a co-solvent.

The tosylation of cellulose in ionic liquids (ILs) was studied. Due to the beneficial effect of different co-solvents, the reaction could be performed at 25°C without the need of heating (in order to reduce viscosity) or cooling (in order to prevent side reactions). The effects of reaction parameters, such as time, molar ratio, and type of base, on the degree of substitution (DS) with tosyl- and chloro-deoxy groups as well as on the molecular weight were evaluated. Products with a DStosyl≤1.14 and DSCl≤0.16 were obtained and characterized by means of NMR- and FT-IR spectroscopy in order to evaluate their purity and distribution of functional groups within the modified anhydroglucose unit (AGU). Tosylation of cellulose in mixtures of IL and a co-solvent was found to result in predominant substitution at the primary hydroxyl group. Size exclusion chromatography (SEC) revealed only a moderate degradation of the polymer backbone at a reaction time of 4-8h. Finally, the nucleophilic displacement (SN) of tosyl- and chloro-deoxy groups by azide as well as recycling of the ILs was studied.

Biofunctional surfaces based on dendronized cellulose.

Biofunctionalized surfaces based on dendronized cellulose were prepared either by embedding 6-deoxy-6-(1,2,3-triazolo)-4-polyamidoamine (PAMAM) cellulose (degree of substitution, DS 0.25), obtained by homogeneous conversion of 6-deoxy-6-azido cellulose with propargyl-PAMAM dendron via the copper-catalyzed Huisgen reaction, in a cellulose acetate (DS 2.50) matrix or by the heterogeneous functionalization of deoxy-azido cellulose film with the dendron. The amount of amino groups provided by the solid supports was determined and the covalent attachment of enzyme was proven with glucose oxidase as model enzyme after activation with glutardialdehyde. The quality of glucose oxidase immobilization was defined by determining of the specific enzyme activity, coupling efficiency, storage stability, and reproducibility. Although the heterogeneous functionalization of the deoxy-azido film yields a product that binds more enzyme compared to the blend of dendronized cellulose derivative with cellulose acetate, the coupling efficiency is comparatively small. Nevertheless, the different approaches for the preparation of biofunctionalized surfaces based on dendronized cellulose provide an excellent reproducibility and good storage stability.

Novel bulky esters of cellulose.

Novel bulky esters of cellulose were synthesized homogeneously, applying the solvent systems DMA/LiCl or DMSO/TBAF, by conversion of the biopolymer with aryl polyester dendrons. The carboxylic acid moieties were efficiently activated in situ with CDI or the acid chloride was applied. Cellulose esters with DS values of up to 0.7 were obtained. The functionalization pattern was analyzed by different NMR spectroscopic techniques indicating that not only position 6 (primary hydroxyl group) but also the secondary one at position 2 was included in the reaction.