PL226585B1 - Multifunctional chitin ‑ lignin biomaterials and the method of their preparation - Google Patents

Description

Description of the invention

The subject of the invention is multifunctional chitin-lignin biomaterials and the method of their preparation. They are used, inter alia, in as polymer fillers, active biosorbents in environmental protection for the removal of inorganic and / or organic pollutants, carriers of organic compounds or innovative electrode materials.

The growing demand for new, precisely designed biomaterials with desired chemical, physical and mechanical properties is a factor influencing the development of research related to the preparation and potential application of natural macromolecular polymers, which in the long term can be used in various fields of science and industry. Numerous literature reports indicate trends related to the development of research, primarily on the use of lignin as a precursor emerging from the broadly understood biomass and chitin derived from fungal cell walls and shellfish skeletons (e.g. crabs, lobsters, shrimps).

Lignin is a natural polymer found in the cell walls of plants, especially woody plants. It is characterized by an aromatic, three-dimensional structure. There are many theories about its detailed structure and methodology of synthesis, but researchers agree on the essence of the process, which is the polymerization of three monolignols: p-coumarin, coniferyl and sinapine alcohols. In the structure of lignin, ether bonds and C-C bonds [N. Mansouri, J.

Salvadó. Structural characterization of technical lignins for the production of adhesives: Application to lignosulfonate, Kraft, soda-anthraquinone, organosolv and ethanol process lignins. Indium. Crop. Prod. 24 (2006) 8). In addition, it is characterized by the presence of numerous functional groups, including hydroxyl, carboxyl, carbonyl, methoxy and ester. The structure of lignin determines its properties and implies potential application directions [C.G. Boeriu, D. Bravo, R.J.A. Gosselink et al. Characterization of structure-dependent functional properties of lignin with infrared spectroscopy. Indium. Crop. Prod. 20 (2004) 205]. Properly activated lignin is used in the production of biomaterials [F. Monteil-Rivera, M. Phuong, M. Ye et al. Isolation characterization of herbaceous lignins for applications in biomaterials. Indium. Crop. Prod. 41 (2013) 356], adsorbents (PJ Carrott, MM Ribeiro Carrott. Lignin - from natural adsorbent to activated carbon: A review. Bioresource Technol. 98 (2007) 2301], surfactants and dispersants [G. Shulga, V. Shakels, S. Skudra et al, Modified lignin as an environmentally friendly surfactant. Environment. Technology. Resources. Proceedings of the 8th International Scientific and Practical Conference 1 (2011) 276] and in electrochemistry [G. Milczarek, O. Inganas . Renewable cathode materials from biopolymer / conjugated polymer interpenetrating networks. Science 335 (2012) 1468] Products based on raw materials of natural origin, including lignin, are additionally biodegradable, which makes research on this biopolymer part of the so-called field of "green chemistry".

Chitin, on the other hand, is the second most widespread polysaccharide on Earth, built of N-acetylglucosamine units linked by a 3-1,4-glycosidic bond. Chitin is a material that builds the skeletons of fungi, crustaceans, insects, sea sponges, however, on an industrial scale, this compound is obtained mainly from food industry waste [M. Rinaudo. Chitin and chitosan: Properties and applications. Threshold. Polym. Sci. 31 (2006) 603]. The enormous interest in this biopolymer observed in recent years results from the attempts to manage huge amounts of waste from the food industry, but mainly due to the unique properties of chitin, such as biodegradability, biocompatibility, and the ability to adsorb dyes [H. Tang, W. Zhou, L. Zhang. Adsorption isotherms and kinetics studies of malachite green on chitin hydrogels J. Hazard. Mater. 209-210 (2012) 218] and metal complexation, and affinity for enzymes. All these properties contribute to the use of chitin in many industries, including as an adsorbent in modern wastewater treatment technologies [P.X. Pinto, S.R. Al-Abed, D.J. Reisman. Biosorption of heavy metals from mining influenced water onto chitin products. Chem. Eng. J. 166 (2011) 1002], biodegradable composites and polymeric materials, but also in the design of bioresorbable bone substitutes [R. Jayakumar, K.P. Chennazhi, S. Srnivasan et al. Chitin scaffolds in tissue engineering. Int. J. Mol. Sci. 12 (2011) 1876], drug distribution systems [R. Jayakumar, A. Nair, N. Sanoj Rejinold et al. Doxorubicin-loaded pH-responsive chitin nanogels for drug delivery to cancer cells. Carbohydrate Polym. 87 (2012) 2352] or dressing materials. The presence of reactive functional groups in the chitin molecule, such as -OH, -C = O, or -NH creates a great opportunity to carry out modifications

PL 226 585 B1 in order to design new materials with defined performance properties that translate into their wide range of applications. Therefore, in the present invention, an attempt was made to create a group of products based on lignin and chitin with defined physicochemical and dispersion-morphological properties.

Patent application CN 10851429 is known in the available sources, which discloses a method of obtaining a composite material containing lignin, chitin, plasticizer, antioxidant, flame retardant mixture, which is a mechanical combination of components without their chemical interaction for use in polymers. The two-component material consisting of chitosan (a synthetic derivative of chitin) and lignin, forming a biodegradable film, is also the basis of patent application CN 101220176 A. This combination of chitosan, which is a completely different component than chitin, and lignin, in which the lignin content is 5-30% by weight. it is not a chemical interaction between components, it is merely a mixture of components from a chemical point of view. The produced system, or in fact the mixture of components, has potential application in biodegradable membranes. The assumption of the authors of the present invention is, firstly, to obtain a completely different system, because it is the chitin-lignin biomaterial, and secondly, the components interact chemically, which indicates that they are connected with each other by permanent chemical bonds (covalent bonds), which from the point of view of the authors of the patent application CN 101220176 A, it was irrelevant and has not been achieved.

In each of the cases known in the state of the art, products with defined physicochemical properties are obtained, however, from the point of view of the authors of this patent application, a biomaterial consisting only of chitin and lignin, most preferably in a 5: 1 ratio, obtained with the use of a ball mill and strong oxidants, as activators of the biopolymers used, may have the most favorable physicochemical, morphological and microstructural properties, which will allow it to be used as a multifunctional polymer filler, an active biosorbent in environmental protection, to remove inorganic and / or organic pollutants, a carrier of organic compounds or an innovative electrode material .

The essence of the invention are multifunctional chitin-lignin biomaterials, characterized in that they are chitin, preferably alpha-chitin, and lignin, preferably kraft lignin, in various weight ratios of chitin: lignin, preferably in a 5: 1 ratio, additionally for the purpose of chemical combination components, 3-75% by weight, preferably 30% by weight, of strong oxidants such as hydrogen peroxide or disodium nitrosodisulfonate, or dipotassium nitrosodisulfonate, or potassium permanganate or sodium periodate or potassium periodate, or ozone, preferably hydrogen peroxide, are added. on the fact that the biomaterials are mechanically ground, preferably using a ball mill, in a chitin: lignin weight ratio of 5: 1 with the addition of strong oxidants, and then dried, while the process of obtaining chitin-lignin biomaterial is carried out at a temperature of 15-85 ° C, preferably 25 ° C.

Thanks to the solution according to the invention, the following technical and operational effects were obtained:

• the obtained biomaterials are characterized by a diversified surface morphology and a significant particle size distribution, • chitin-lignin products obtained by the proposed method show high electrokinetic and steric stability, • the obtained systems are also characterized by defined thermal and colorimetric properties, • the possibility of using chitin-lignin systems as biosorbents enabling the adsorption process (e.g. heavy metal ions, dyes, phenol and its derivatives), as functional biomaterials in many fields and as carriers of active substances and enzymes.

The invention in an exemplary embodiment has been illustrated in the figures and tables, where Fig. 1 shows an electron microscopy photo of the chitin-lignin biomaterial, Fig. 2 shows the particle size distribution taking into account the volume fraction, Fig. 3 shows a microscopic-electron photo of the chitin-lignin biomaterial Fig. 4 shows the particle size distribution taking into account the volume fraction in the graph, Fig. 5 shows the electron microscopy photograph of the chitin-lignin biomaterial, Fig. 6 shows the particle size distribution taking into account the volume fraction, Fig. 7 shows the electron microscopy photo of the chity4 biomaterial

N-lignin, Fig. 8 is a graph of the particle size distribution taking into account the volume fraction, Fig. 9 is an electron microscopy photograph of the chitin-lignin biomaterial, Fig. 10 is a graph of the particle size distribution taking into account the volume fraction, Table 1 shows dispersion parameters for the obtained biomaterial, Table 2 shows the percentage of the elements.

The following examples illustrate the invention:

P r z k ł a d I

In order to combine alpha-chitin and kraft lignin, it was proposed to mechanically crush the starting reagents with simultaneous mixing using a centrifugal ball mill.

₃

To 5 g of alpha-chitin and 5 g of kraft lignin, 10 cm ^{3 of} 15% hydrogen peroxide was added, and then the system prepared in this way with the balls was closed in a grinding container. In order to obtain the appropriate homogeneity of the final material, grinding took 5 hours. After the milling process was finished, the system was placed in a stationary dryer and convectionally dried at the temperature of 105 ° C for about 24 hours.

Fig. 1 is an electron microscopy photograph of a chitin-lignin biomaterial obtained in the above manner. Fig. 2 shows the particle size distribution taking into account the volume fraction, and in Table 1 the dispersion parameters for the obtained biomaterial. Table 2 shows the percentage of the elements in the obtained product.

Example II ₃

1 g of beta-chitin and 5 g of kraft lignin were used, to which 10 cm ^{3 of} 15% hydrogen peroxide was added, and then the whole was placed in a ball mill. The process of obtaining the final chitin-lignin product was carried out as in Example I.

Fig. 3 is an electron microscopy photograph of chitin-lignin biomaterial obtained in the above manner. Figure 4 shows the particle size distribution taking into account the volume fraction, and Table 1 shows the dispersion parameters of the product obtained. Table 2 presents the percentage of the elements in the obtained system.

Example III ₃

5 g of alpha-chitin and 1 g of kraft lignin were used, to which 10 cm ^{3 of} 20% hydrogen peroxide was added, and then the whole was placed in a ball mill. The process of obtaining the final chitin-lignin product was carried out as in Example I.

Fig. 5 is an electron microscopy photo of chitin-lignin biomaterial obtained in the above manner. Figure 6 shows the particle size distribution based on the volume fraction, and Table 1 shows the dispersion parameters of the product obtained. Table 2 presents the percentage of the elements in the obtained system.

P r x l a d IV

In order to combine alpha-chitin and kraft lignin, a process of mechanical grinding of the starting reagents with simultaneous mixing using a mortar grinder was proposed. ^{10 cm 3 of} 15% hydrogen peroxide was added to 5 g of ₃ alpha-chitin and 5 g of kraft lignin, and then the system prepared in this way was placed in a mortar grinder. In order to obtain the appropriate homogeneity of the final material, grinding took 3 hours. After the grinding process was completed and simultaneous mixing, the system was placed in a stationary dryer and convectionally dried at 105 ° C for about 24 hours.

Fig. 7 shows an electron microscopy photograph of a chitin-lignin biomaterial obtained in the above manner. Fig. 8 shows the particle size distribution taking into account the volume fraction, and in Table 1 the dispersion parameters for the obtained biomaterial. Table 2 shows the percentage of the elements in the obtained product.

P r z k ł a d V

In order to combine alpha-chitin and kraft lignin, it was proposed to mechanically crush the starting reagents with simultaneous mixing using a centrifugal ball mill. 5 g of alpha-chitin was added to 5 g of Kraft's lignin, and then the system and the balls were sealed in a grinding container. In order to obtain the appropriate homogeneity of the final material, grinding took 5 hours. After the grinding process was finished, the system was placed in a stationary dryer and convection drying at the temperature of 105 ° C for about 24 hours.

Fig. 9 shows an electron microscopy photograph of a chitin-lignin biomaterial obtained in the above manner. Fig. 10 shows the particle size distribution taking into account the volume fraction, and in Table 1 the dispersion parameters for the obtained biomaterial. Table 2 shows the percentage of the elements in the obtained product.

Claims (2)

Patent claims 1. Multifunctional chitin-lignin biomaterials, characterized in that they are chitin, preferably alpha-chitin, and lignin, preferably kraft lignin in various weight ratios of chitin: lignin, preferably in a 5: 1 ratio, additionally added to chemically combine the components 3-75 wt.%, preferably 30 wt.% of strong oxidants of the type hydrogen peroxide or disodium nitrosodisulfonate or dipotassium nitrosodisulfonate or potassium permanganate or sodium periodate or potassium periodate or ozone, preferably hydrogen peroxide. 2. The method of obtaining multifunctional chitin-lignin biomaterials, characterized in that the biomaterials are mechanically ground, preferably with the use of a ball mill, in a weight ratio of chitin: lignin equal to 5: 1 with the addition of strong oxidants, and then dried, the process of obtaining chitin biomaterial -lignin is carried out at a temperature of 15-85 ° C, preferably 25 ° C.