The world population is growing exponentially. At the same time, the availability of natural resources decreases dramatically – an alarming trend which demands for a sustainable use of our resources in a circular economic framework and hence, for the valorization of wastes and by-products. Owing to its high annual abundance, lignocellulosic biomass has a promising potential as renewable resource for the development of high-value products, covering fuels, platform chemicals, and specialty polymers. Besides, lignocelluloses offer an attractive basis for material applications, considering their peculiarity as natural composites and their inherent modifiability. Therefore, targeted chemical modifications have been widely used to exploit this potential and to further increase their spectrum of characteristics and application prospects. The objective of this study was to fabricate lignocellulose-based hydrogels, with the prospect to be used as soil conditioners in agriculture. Considering this application, this study was striving for the development of a simple synthetic pathway that ideally guarantees non-toxic and biodegradable products. Besides, two key factors were involved in the development of the synthetic route and constitute the center of this study: the accessibility of lignocelluloses towards chemical modifications – in view of their inherent recalcitrance – and the envisaged properties of the hydrogel, including high swelling rates and structural stability. To comply with both key factors, three basic processing steps were carried out: (1) feedstock activation by chemical or mechanical pretreatments, (2) introduction of ionic groups to induce swelling properties and (3) gel network formation via chemical crosslinking. Furthermore, to elucidate the behavior of different biomass types, wheat straw and beech sawdust were exemplarily surveyed. In the first step, different chemical (ozonolysis, alkaline and sulfite pulping) or mechanical (short-time ball milling) pretreatment approaches were used to activate the feedstocks by inducing compositional and/or structural alterations. In the second processing step, two modification reactions – carboxymethylation and phosphorylation (with phosphoric acid/molten urea) – were examined with emphasis on their ability to access lignocellulosic matrices and to realize high contents of ionic groups. In the final step, covalently crosslinked gel networks were formed using either citric acid or electron beam irradiation. Both crosslinking approaches were evaluated in detail with respect to yield and properties of the resulting hydrogels. In view of the two key factors proposed for this study – the accessibility of lignocelluloses and the final hydrogel properties – and amongst the approaches examined, the following synthetic pathway delivered the most promising results: ball milling ⟶ carboxymethylation ⟶ citric acid crosslinking. In this process, the promoting effect of ball milling can be attributed to particle size reduction, a breakdown of plant cell structures, and a decline of the cellulose crystallinity. The effectivity of carboxymethylation was particularly based on its alcoholic-alkaline media. Therefore, the uptake of alkali induced a partial disintegration of the lignocellulosic matrix, facilitating both the introduction of ionic groups and high swelling rates of the final gels. Overall, this path delivered promising results for straw-based gels, whereas beech sawdust was hardly accessible.

The world population is growing exponentially. At the same time, the availability of natural resources decreases dramatically – an alarming trend which demands for a sustainable use of our resources in a circular economic framework and hence, for the valorization of wastes and by-products. Owing to its high annual abundance, lignocellulosic biomass has a promising potential as renewable resource for the development of high-value products, covering fuels, platform chemicals, and specialty polymers. Besides, lignocelluloses offer an attractive basis for material applications, considering their peculiarity as natural composites and their inherent modifiability. Therefore, targeted chemical modifications have been widely used to exploit this potential and to further increase their spectrum of characteristics and application prospects. The objective of this study was to fabricate lignocellulose-based hydrogels, with the prospect to be used as soil conditioners in agriculture. Considering this application, this study was striving for the development of a simple synthetic pathway that ideally guarantees non-toxic and biodegradable products. Besides, two key factors were involved in the development of the synthetic route and constitute the center of this study: the accessibility of lignocelluloses towards chemical modifications – in view of their inherent recalcitrance – and the envisaged properties of the hydrogel, including high swelling rates and structural stability. To comply with both key factors, three basic processing steps were carried out: (1) feedstock activation by chemical or mechanical pretreatments, (2) introduction of ionic groups to induce swelling properties and (3) gel network formation via chemical crosslinking. Furthermore, to elucidate the behavior of different biomass types, wheat straw and beech sawdust were exemplarily surveyed. In the first step, different chemical (ozonolysis, alkaline and sulfite pulping) or mechanical (short-time ball milling) pretreatment approaches were used to activate the feedstocks by inducing compositional and/or structural alterations. In the second processing step, two modification reactions – carboxymethylation and phosphorylation (with phosphoric acid/molten urea) – were examined with emphasis on their ability to access lignocellulosic matrices and to realize high contents of ionic groups. In the final step, covalently crosslinked gel networks were formed using either citric acid or electron beam irradiation. Both crosslinking approaches were evaluated in detail with respect to yield and properties of the resulting hydrogels. In view of the two key factors proposed for this study – the accessibility of lignocelluloses and the final hydrogel properties – and amongst the approaches examined, the following synthetic pathway delivered the most promising results: ball milling ⟶ carboxymethylation ⟶ citric acid crosslinking. In this process, the promoting effect of ball milling can be attributed to particle size reduction, a breakdown of plant cell structures, and a decline of the cellulose crystallinity. The effectivity of carboxymethylation was particularly based on its alcoholic-alkaline media. Therefore, the uptake of alkali induced a partial disintegration of the lignocellulosic matrix, facilitating both the introduction of ionic groups and high swelling rates of the final gels. Overall, this path delivered promising results for straw-based gels, whereas beech sawdust was hardly accessible.