Kinetics and mechanism of urea - formaldehyde and related reactions

Urea-formaldehyde resins find numerous applications in adhesive, textile finishing and moulded plastic industries. Kinetic investigations of the reactions of urea and its related compounds with formaldehyde in aqueous acid, alkaline and neutral media have been carried out. A thin—layer chromatographic method was developed for the separation and estimation of the products of these reactions. Using this technique the various initial steps in the reactions were analysed and the rate constants have been determined.

Urea formaldehyde foam insulation.

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Genotoxic effects in occupational exposure to formaldehyde: A study in anatomy and pathology laboratories and formaldehyde-resins production

ABSTRACT – Background: According to the Report on Carcinogens, formaldehyde ranks 25th in the overall U.S. chemical production, with more than 5 million tons produced each year. Given its economic importance and widespread use, many people are exposed to formaldehyde environmentally and/or occupationally. Presently, the International Agency for Research on Cancer classifies formaldehyde as carcinogenic to humans (Group 1), based on sufficient evidence in humans and in experimental animals. Manyfold in vitro studies clearly indicated that formaldehyde can induce genotoxic effects in proliferating cultured mammalian cells. Furthermore, some in vivo studies have found changes in epithelial cells and in peripheral blood lymphocytes related to formaldehyde exposure. Methods: A study was carried out in Portugal, using 80 workers occupationally exposed to formaldehyde vapours: 30 workers from formaldehyde and formaldehyde-based resins production factory and 50 from 10 pathology and anatomy laboratories. A control group of 85 non-exposed subjects was considered. Exposure assessment was performed by applying simultaneously two techniques of air monitoring: NIOSH Method 2541 and Photo Ionization Detection equipment with simultaneously video recording. Evaluation of genotoxic effects was performed by application of micronucleus test in exfoliated epithelial cells from buccal mucosa and peripheral blood lymphocytes. Results: Time-weighted average concentrations not exceeded the reference value (0.75 ppm) in the two occupational settings studied. Ceiling concentrations, on the other hand, were higher than reference value (0.3 ppm) in both. The frequency of micronucleus in peripheral blood lymphocytes and in epithelial cells was significantly higher in both exposed groups than in the control group (p < 0.001). Moreover, the frequency of micronucleus in peripheral blood lymphocytes was significantly higher in the laboratories group than in the factory workers (p < 0.05). A moderate positive correlation was found between duration of occupational exposure to formaldehyde (years of exposure) and micronucleus frequency in peripheral blood lymphocytes (r = 0.401; p < 0.001) and in epithelial cells (r = 0.209; p < 0.01). Conclusions: The population studied is exposed to high peak concentrations of formaldehyde with a long-term exposure. These two aspects, cumulatively, can be the cause of the observed genotoxic endpoint effects. The association of these cytogenetic effects with formaldehyde exposure gives important information to risk assessment process and may also be used to assess health risks for exposed worker

Physical and mechanical properties of particleboard bamboo waste bonded with urea formaldehyde and castor oil based adhesive

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Cisalhamento na Linha de Cola de Compensados de Eucalyptus sp. e Adesivo PVA

Studies on new adhesives and resins for bonding wood and wood products are being carried out with the intention to improve their properties, taking into account a lower environmental impact. To this end, new formulations of polyvinyl acetate (PVA) adhesives have been developed, because they have no polluting harmful to health chemicals in their composition, in contrast to formaldehyde-based resins; which in turn are the most commonly used for wood panels production these days. This study tested three different formulations of PVA adhesives, with different pressing times and temperatures for the production of Eucalyptus sp. plywood, obtaining satisfactory results with respect to shear strength at the bondline, which was higher for the PVA adhesives compared to the urea-formaldehyde and phenol-formaldehyde panels found in the literature.

Produção e caracterização físico-mecânica de painel de compensado de Eucalyptus sp. e adesivo PVA

Studies on new adhesives and resins for bonding wood and wood products are being conducted with the intention of improving their properties, taking into account a lower environmental impact. For this reason new formulations of polyvinyl acetate (PVA) adhesives have been developed, because they have no chemicals in its composition extremely polluting and harmful to health, as is the case of formaldehyde-based resins, which in turn are the most commonly used today for wood panels production. This study tested three different formulations of PVA adhesives, with different times and temperatures of pressing for the production of Eucalyptus sp. Plywood, coming up in satisfactory results with respect to shear strength at the bondline, which was higher for the PVA adhesives compared with urea-formaldehyde and phenol. The results of MOE and MOR were lower than those values of the panels produced with urea and phenol-formaldehyde, and the results of physical tests showed to be close to the panels produced with these same adhesives

Uma revisão sobre a resina uréia-formadeído (RUF) empregada na produção de painéis de madeira reconstituída

According to ABIPA (2009), Brazil is currently among the major producers of reconstituted wood panels, with one of the main factors for this condition, its climate and its large land area, which allows the cultivation of forests, which provide raw materials for these industries. To establish that market as power, Brazil has invested about R$ 1.3 billion in the last 10 years, yet designed an investment of 0.8 billion dollars over the next three years (BNDES, 2008). With the new investments in this segment, we expect a growth of about 66% in the resin consumption of urea-formaldehyde (GPC, 2009) which should also result in major investments by the companies producing this polymer. Currently employees are mainly three types of resins in the production industry panels, as follows: Urea-Formaldehyde Resin (R-UF), melamine-formaldehyde resin (R-MF) and Phenol-Formaldehyde Resin (R-FF). Especially the cost factor, the urea-formaldehyde resin is the most used by companies producing reconstituted wood panels. The UF-R is a polymer obtained by condensation of urea and formaldehyde reactors (usually batch type), characterized by being a thermosetting polymer which makes it very efficient for bonding wood composites. The urea-formaldehyde polymer, to present a quite complex, it becomes very difficult to predict the exact chain resulting in the process of condensation of urea with formaldehyde, so that a greater knowledge of its characteristics and methods for their characterization can result in greater control in industrial processes and subsequent decrease cost and improve the quality of reconstituted wood panels produced in Brazil

Estudo da influência das resinas termofixas uréia formaldeído (UF) e melamina formaldeído (MF) nas características físicas e mecânicas de painéis MDF

Thermosetting resins are very important in the production of MDF panels. They act as an adhesive in the process of compacting and consolidating the fiberboard. Thermoset resins commonly used in this process are based resin urea formaldehyde (UF) and melamine formaldehyde (MF). The first has a higher demand due to its low cost and good performance in meeting the specifications and standards. The second has a high cost compared to MF resin, but adds greater value to the MDF panel, because it gives greater moisture resistance. The process of manufacture of MDF boards was briefly presented in this study to facilitate the understanding of the work. Samples of thermosetting resins (UF and MF) were subjected to physical-chemical seeking to relate these results to the technological performance presented by their respective samples of MDF boards. Two other samples of MDF panels were subjected to physical and mechanical tests. Results were analyzed and related to the award of their respective thermoset resin. Instruments like Dahmos Trend Manager ® and Grecon Dax 5000 and TG - DSC analysis were used in this study to assist in the analysis of the results. It was observed that the results of the analysis of thermosetting resins were within the specified. Such resins do not directly influence the technological tests provided by the MDF panels, but it has been found that the process variables such as humidity and fiber production rate interfere with the performance of the resin accelerating the reaction and therefore their influence on the physical-mechanical properties of the panels MDF. Samples of MDF panels with UF and MF met all the specifications required by the Brazilian standard with regard to the technological quality. The increased demand for UF resin market is justified by the service specifications...

Evaluation of bamboo particleboards produced with urea-formaldheyde resin

The bamboo waste can be an alternative material to sustain the crescent demand for particleboards, also bringing ecological benefits as reduction of the pressure for raw materials and landfill space demands. In this context, this research aimed to manufacture and determine some physical and mechanical properties of particleboards with bamboo waste particles (Dendrocalamus giganteus), obtained from different sources, bonded with four different percentages of urea–formaldehyde (UF) based resin (6%, 8%, 10% and 12% related to dry material of particles). Response variables investigated were: density; moisture content; thickness swelling in 2 and 24 hours; water absorption in 2 and 24 hours; internal adhesion (STpe); strength in tension parallel to faces (STpa); modulus of elasticity (MOE) and modulus of rupture (MOR). Results permitted to conclude that particleboards as mentioned showed good performance only in the physical properties requirements imposed by Brazilian Standard NBR 14810, but this was not observed to mechanical properties considered. New researches are needed in order to optimize the producing process parameters.

Production of phenol-formaldehyde resin composites

The main objective of this work was to examlne the various stages of the production of industrial laminates based on phenol-formaldehyde resins, with a view of suggesting ways of improving the process economics and/or the physical properties of the final product. Aspects of impregnation, drying, and lamination were investigated. The resins used in all experiments were ammonia-catalysed. Work was concentrated on the lamination stage since this is a labour intensive activity. Paper-phenolic lay-ups were characterised in terms of the temperatures experienced during cure, and a shorter cure-cycle is proposed, utilising the exothermic heat produced during pressing of 25.5 mm thick lay-ups. Significant savings in production costs and improvements in some of the physical properties have been achieved. In particular, water absorption has been reduced by 43-61%. Work on the drying stage has shown that rapid heating of the wet impregnated substrate results in resin solids losses. Drying at lower temperatures by reducing the driving force leads to more resin (up to 6.5%) being retained by the prepregs and therefore more effective use of an expensive raw material. The impregnation work has indicated that residence times above 6 seconds in the varnish bath enhance the insulation resistance of the final product, possibly due to improved resin distribution and reduction in water absorption. In addition, a novel process which involves production of laminates by in situ polymerisation of the phenolic resin on the substrate has been examined. Such a process would eliminate the solvent recovery plant - a necessary stage in current industrial processes. In situ polymerisation has been shown to be chemically feasible.

Production of renewable phenolic resins by thermochemical conversion of biomass: a review

This review covers the production and utilisation of liquids from the thermal processing of biomass and related materials to substitute for synthetic phenol and formaldehyde in phenol formaldehyde resins. These resins are primarily employed in the manufacture of wood panels such as plywood, MDF, particle-board and OSB. The most important thermal conversion methods for this purpose are fast pyrolysis and vacuum pyrolysis, pressure liquefaction and phenolysis. Many feedstocks have been tested for their suitability as sources of phenolics including hard and softwoods, bark and residual lignins. Resins have been prepared utilising either the whole liquid product, or a phenolics enriched fraction obtained after fractional condensation or further processing, such as solvent extraction. None of the phenolics production and fractionation techniques covered in this review are believed to allow substitution of 100% of the phenol content of the resin without impacting its effectiveness compared to commercial formulations based on petroleum derived phenol. This survey shows that considerable progress has been made towards reaching the goal of a price competitive renewable resin, but that further research is required to meet the twin challenges of low renewable resin cost and satisfactory quality requirements. Particular areas of concern are wood panel press times, variability of renewable resin properties, odour, lack of reactive sites compared to phenol and potential for increased emissions of volatile organic compounds.

Activation of waste MDF sawdust charcoal and its reactive dye adsorption characteristics

This paper reports an experimental investigation of converting waste medium density fibreboard (MDF) sawdust into chars and activated carbon using chemical activation and thermal carbonisation processes. The MDF sawdust generated during the production of architectural mouldings was characterised and found to have unique properties in terms of fine particle size and high particle density. It also has a high content of urea formaldehyde resin used as a binder in the manufacturing of MDF board. Direct thermal carbonisation and chemical activation of the sawdust by metal impregnation and acid (phosphoric acid) treatment prior to pyrolysis treatment were carried out. The surface morphology of the raw dust, its chars and activated carbon were examined using scanning electron microscopy (SEM). Adsorptive properties and total pore volume of the materials were also analysed using the BET nitrogen adsorption method. Liquid adsorption of a reactive dye (Levafix Brilliant red E-4BA) by the derived sawdust carbon was investigated in batch isothermal adsorption process and the results compared to adsorption on to a commercial activated carbon (Filtrasorb F400). The MDF sawdust carbon exhibited in general a very low adsorption capacity towards the reactive dye, and physical characterisation of the carbon revealed that the conventional chemical activation and thermal carbonisation process were ineffective in developing a microporous structure in the dust particles. The small size of the powdery dust, the high particle density, and the presence of the urea formaldehyde resin all contributed to the difficulty of developing a proper porous structure during the thermal and chemical activation process. Finally, activation of the dust material in a consolidated form (cylindrical pellet) only achieved very limited improvement in the dye adsorption capacity. This original study, reporting some unexpected outcomes, may serve as a stepping-stone for future investigations of recycle and reuse of the waste MDF sawdust which is becoming an increasing environmental and cost liability. (C) 2004 Elsevier Ltd. All rights reserved.

Valorization of an Industrial Organosolv-Sugarcane Bagasse Lignin: Characterization and Use as a Matrix in Biobased Composites Reinforced With Sisal Fibers

In the present study, the main focus was the characterization and application of the by-product lignin isolated through an industrial organosolv acid hydrolysis process from sugarcane bagasse, aiming at the production of bioethanol. The sugarcane lignin was characterized and used to prepare phenolic-type resins. The analysis confirmed that the industrial sugarcane lignin is of HGS type, with a high proportion of the less substituted aromatic ring p-hydroxyphenyl units, which favors further reaction with formaldehyde. The lignin-formaldehyde resins were used to produce biobased composites reinforced with different proportions of randomly distributed sisal fibers. The presence of lignin moieties in both the fiber and matrix increases their mutual affinity, as confirmed by SEM images, which showed good adhesion at the biocomposite fiber/matrix interface. This in turn allowed good load transference from the matrix to the fiber, leading to biobased composites with good impact strength (near 500 J m(-1) for a 40 wt% sisal fiber-reinforced composite). The study demonstrates that sugarcane bagasse lignin obtained from a bioethanol plant can be used without excessive purification in the preparation of lignocellulosic fiber-reinforced biobased composites displaying high mechanical properties. Biotechnol. Bioeng. 2010;107: 612-621. (C) 2010 Wiley Periodicals, Inc.

Prospects for the use of municipal tree pruning wastes in particleboard production

The purpose of this study was to evaluate the physical and mechanical properties of particleboard made with pruning wastes from Ipê (Tabebuia serratifolia) and Chapéu-de-Sol (Terminalia catappa) trees. Particleboards were prepared with both wood species, using all the material produced by grinding the pruning wastes. The particleboards had dimensions of 45×45 cm, a thickness of approximately 11.5 mm and an average density of 664 kg/m3. A urea-formaldehyde adhesive was used in the proportion of 12% of the dry particle mass. The particleboards were pressed at a temperature of 130 C for 10 mins. The physical and mechanical properties analyzed were density, moisture content, thickness swelling, percentage of lignin and cellulose, modulus of resilience, modulus of elasticity and tensile strength parallel to the grain, accordingly to the standards NBR 14810 and CS 236-66 (1968). The particleboards were considered to be of medium density. The particle size significantly affected the static bending strength and tensile strength parallel to the grain. Ipê presented better results, demonstrating a potential for the production and use of particleboard made from this species. © The Author(s) 2013.