The cell walls of woody plants are compounded materials made by in situ polymerization of a polyphenolic matrix (lignin) into a web of fibers (cellulose), a process that is catalysed by polyphenoloxidases (laccases) or peroxidases. The first attempt to transform the basic strategy of this natural process for use in human craftsmanship was the ancient lacquer method. The sap of the lacquer tree (Rhus verniciflua) contains large amounts of a phenol (urushiol), a polysaccharide and the enzyme laccase. This oil-in-water emulsion solidifies in the presence of oxygen. The Chinese began using this phenomenon for the production of highly creative artwork more than 6,000 years ago. It was the first example of an isolated enzyme being used as a catalyst to create an artificial plastic compound. In order to apply this process to the production of products on an industrial scale, an inexpensive phenol must be used, which is transferred by an enzyme to active radicals that react with different components to form a compounded material. At present, the following approaches have been studied: (1) In situ polymerization of lignin for the production of particle boards. Adhesive cure is based on the oxidative polymerization of lignin using phenoloxidases (laccase) as radical donors. This lignin-based bio-adhesive can be applied under conventional pressing conditions. The resulting particle boards meet German performance standards. By this process, 80% of the petrochemical binders in the wood-composite industry can be replaced by materials from renewable resources. (2) Enzymatic copolymerization of lignin and alkenes. In the presence of organic hydroperoxides, laccase catalyses the reaction between lignin and olefins. Detailed studies on the reaction between lignin and acrylate monomers showed that chemo-enzymatic copolymerization offers the possibility to produce defined lignin-acrylate copolymers. The system allows control of the molecular weights of the products in a way that has not been possible with chemical catalysts. This is a novel attempt to enzymatically induce grafting of polymeric side chains onto the lignin backbone, and it enables the utilization of lignin as part of new engineering materials. (3) Enzymatic activation of the middle-lamella lignin of wood fibers for the production of wood composites. The incubation of wood fibers with a phenol oxidizing enzyme results in oxidative activation of the lignin crust on the fiber surface. When such fibers are pressed together, boards are obtained which meet the German standards for medium-density fiber boards (MDF). The fibers are bound together in a way that comes close to that by which wood fibers are bound together in naturally grown wood. This process will, for the first time, yield wood composites that are produced solely from naturally grown products without any addition of resins.
Increasing prices of petrochemical resins and possible harmful formaldehyde emissions from conventionally produced wood composites have resulted in increased interest in enzymatic binder systems as environmentally friendly alternatives for gluing lignocellulosic products. In this study, laccase mediator systems (LMSs) were used to activate lignin on wood fiber surfaces in the pilot-scale production of medium-density fiberboard (MDF) using a dry process. Three different mediators were applied: 4-hydroxybenzoic acid (HBA), 1-hydroxybenzotriazole (HBT), and acetosyringone (AS) of which HBA performed best. The mechanical properties of the manufactured boards produced with thermomechanical pulp (TMP) fibers, laccase, and HBA fulfilled all required European standards for wood-based panels. Oxygen consumption rates of the different LMSs and (13)C NMR spectroscopy results for treated TMP fibers were obtained for qualitative and quantitative analysis of lignin activation. The results show that reactions were most effective within the first 30 min of incubation. Oxygen consumption was fastest and highest for the LMS using HBA. (13)C NMR spectroscopy indicated the highest decrease of aromatic groups in the wood fiber lignin with this LMS. The data correlated well with the quality of the MDF. The required enzymatic reaction times allowed direct integration of the LMS into standard MDF production techniques. The results indicate that application of LMSs has a high potential for environmentally friendly MDF production.
In this study, a new technical process for hardening wood fiber insulation boards is introduced. During the dry-process, the fibers are usually glued with polymeric-diphenylmethane-diisocyanate (pMDI) and hardened to wood fiber insulation boards using a steam-air mixture. However, the maximum temperature reached in the steam-air process was 100 °C, and it was impossible to use an alternative binding agent for the gluing of the wood fiber insulation boards other than pMDI. When incubated with laccase-mediator-system (LMS) as a naturally based bonding system, temperatures of over 120 °C are required because of the chemical wood composition, especially the lignin. In this case, the hot-air/hot-steam process offers new technical opportunities for realizing temperatures above 100 °C. In this study, wood fiber insulation boards were glued with LMS, vs. reference boards with inactivated LMS, laccase alone, and 4% pMDI. Then, the boards were hardened using one of three processes: with steam-air mixture, with hot-air, and with hot-air/hot-steam. Through the hot-air/hot-steam process, temperatures of well over 120 °C were attainable. All the insulation boards hardened using the hot-air/hot-steam process showed better physical and technical properties than those hardened with steam-air mixture or hot-air alone. The reason for this is a sudden increase of temperature after the adding of steam because high temperatures insure that the LMS activated wood fiber surface lignins are completely plasticized. As a result the physical-technological properties such as internal bond strength, compression strength, and short term water absorption of insulation boards treated with LMS were comparable to those boards treated with 4% pMDI.Keywords: Wood insulation boards; pMDI Contact information: Faculty of Forest Science and Forest Ecology, Department of Molecular Wood Biotechnology and Technical Mycology, Büsgenweg 2, Goettingen 37077, Germany; *Corresponding author: meuring@gwdg.de INTRODUCTIONIn the production of wood based panels, large quantities of petrochemical binding agents, such as urea formaldehyde or phenol formaldehyde resins, are required (González-Garciá et al. 2011). Besides the dependency on crude oil, harmful formaldehyde is released during the production process as well as out of the products, and this adversely affects ecosystem quality (Imam et al. 1999; US. EPA 2002). Possible solutions are seen in the reduction of those binder systems as well as the replacement by more environmentallyfriendly, natural binders (González-Garciá et al. 2011). Equally, the recycling process of naturally bonded wood products is more efficient (Euring 2008). PEER-REVIEWED ARTICLEbioresources.com Euring et al. (2015). "Hot wood binding with laccase," BioResources 10(2), 3541-3552. 3542In the market of insulation materials, there has been a recent increase in the use of renewable raw materials as insulation in house walls, ceilings, flooring, and roofs due to the Energy Saving Ordinance 2012 in Europe (Brandhorst 2012). In German...
<p class="1Body">Medium density fiberboards (MDF) are produced mainly by urea-formaldehyde resins (UF) as binding agent, which are synthesized from finite fossil resources. Those boards may emit critical amounts of formaldehyde, which can influence the health of humans and animals. In recent times the wood panel board industry is looking for alternative glues which contain less or no formaldehyde. In order to avoid potential formaldehyde emissions altogether it would be preferable not to use binders which are formaldehyde based at all. One possibility is to use natural binders or to activate the wood fibers’ own binding forces by applying Laccase-Mediator-Systems (LMS). As a support of the LMS interactions with wood fibers technical lignin can be added. In this study it was found out that the addition of technical lignin intensified the fiber to fiber bindings. Two Lignin-Laccase-Mediator-Systems (LLMS) were analysed by Gel-Permeation-Chromatography and Cyclic voltammetry. Later the LLMSs were tested in the pilot scale production of MDF. The determination of the physical technological properties revealed that the LLMS treated MDF have higher dimension stabilities than only LMS treated MDF and approximately the same thickness swelling after 24 h. The results indicate that the application of LLMSs have a high potential for natural bonded MDF.</p>
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