PL230478B1 - Method for manufacturing wood-based composite - Google Patents

Description

Description of the invention

The subject of the invention is a method for the production of a wood-based composite meeting the requirements for fire resistance and biological corrosion resistance, applicable as an insulating material for partitions of building walls.

Modern and ecological thermal insulation is aimed at environmental friendliness and improvement of air quality inside the building. More and more attention is paid to insulating materials of organic origin, produced from such renewable resources as: wood shavings, wood fibers, wood wool, cork, linen, hemp, sheep wool, cellulose, reed and straw. These are materials that meet almost 100% of the requirements of sustainable development. The main advantages of thermal insulation made of natural raw materials are: protection of natural resources; environmental friendliness during production; even, almost closed CO2 balance (plants absorb as much CO2 from the atmosphere as they grow when removing waste from these materials); energy saving (a small amount of energy is used to produce this type of insulation); no emission of harmful substances to the atmosphere during use, during waste disposal and material processing; easy waste disposal; short transport route (regional materials). These insulations show very good thermal and humidity properties: they are vapor permeable, have a good thermal capacity and can transport moisture in the material without reducing the thermal power (as evidenced by the high sorption capacity). Such solutions ensure a stable interior microclimate, both in winter and summer. In order to provide these materials with additional functions, flame retardants and agents providing protection against the spread of fire as well as other substances increasing their resistance to biological corrosion may be added to such materials. In the course of appropriate technological processes, the above-mentioned raw materials are properly prepared (dried, crushed, modified, pressed or compacted, etc.). These types of insulation materials, despite various additives and modification processes, remain safe for human health and pose no threat to the surrounding environment. Their great advantage is also good acoustic protection.

From the application P 347325, reinforced composites containing fibers from cellulose pulp dispersed in a matrix are known, in which the matrix contains a polymeric material, preferably a thermoplastic with a melting point above 180 ° C, and the cellulose fibers have a purity with respect to alpha-cellulose greater than 80 % by weight. The invention also includes methods of making and using composites.

According to the patent PL 187621, a method of producing wood-concrete anti-noise boards, especially for free-standing screens protecting against traffic noise, boards whose outer surface is shaped into parallel grooves with side walls symmetrically divergent to the outside, consisting in the preparation of a mass containing cellulose mineralized with calcium chloride cellulose filler and slurry cement and in the subsequent formation of the slab by vibropressing, consists in the fact that coniferous wood is used as cellulose filler, mechanically crushed to the form of rods with a length of 0.4 to 0.9 of the shortest dimension on the sides of the broken line marking the cross-section outline of the grooved slab - in addition to of the side forming the bottom of the groove, rods with a cross-section of 2 to 6 mm and a moisture content not exceeding 20%, the mass of which the board is formed contains in parts by weight: 100 to 140 stamen cellulose filler, 180 to 220 Portland cement, ch calcium lide CaCb 5 to 8, plasticizer 0.5 to 1.5, and water in an amount of 80 to 120 parts by weight.

Description of the invention P. 289227 presents a general purpose non-flammable decorative, insulating and construction panel, which consists of a layer consisting of compacted and entangled non-rot fibers, impregnated on both sides with cement paste, forming an elastic hard skeleton in which there are channels and their load-bearing claddings. The layer is glued on one side to a thin sheet of wood, between the sheet of wood and the skeleton of the fossilized fibers there is a spike shell obtained from a water emulsion of a polymer.

The composite components used in the invention fulfill the following functions:

Wood shavings - particles of lignocellulosic material obtained from pine and / or spruce wood, which are a by-product as a result of mechanical processing of wood intended for other assortments. Wood shavings are an insulating material and thus a substrate for the remaining components of the composite.

PL 230 478 Β1

Proteins - are macromolecular compounds with a specific structure, consisting of long chains of amino acids. They are biopolymers whose monomers are amino acids. All the amino acids included in natural proteins are α-amino acids, and their amino group is bound to the same carbon atom of the molecule to which the carboxyl group is attached. Both the carboxyl group and the amino group are ionized. The first one detaches the proton (H ⁺ ) and converts to the carboxylate anion (-COO). The second, on the other hand, attaches a proton, transforming into an ammonium cation (-NH3 ⁺ ), which in the context of fire protection plays a special role as a blowing agent. Blowing agents are foaming agents - chemical, organic and inorganic substances, which are stable at room temperature and in an inert environment, while at elevated temperature or as a result of the action of appropriate chemicals (even water) they decompose with the release of large amounts of gaseous products (most often nitrogen, oxide carbon (II) and carbon monoxide (IV) and hydrogen. Amino acids, due to the presence of the amino group, promote the formation of a porous structure under combustion conditions by the release of gases: ammonia, carbon dioxide. Spray-dried plasma of blood cells here acts both as an adhesive, enabling permanent deposition of graphite on lignocellulosic particles (wood shavings), as well as an ingredient supporting the fire-retardant effect of wood shavings. Proteins are divided into two broad classes: fibrillar proteins (or fibrous proteins), which are insoluble in water, and globular proteins (otherwise spherical proteins) or glomerulonephritis) that dissolve in water as well as in aqueous solutions of acids, bases and salts, which was presented in the publication of Mazela B. (2008): Perspectives for increasing the durability of wood in terms of environmental protection requirements, Publishing House of the University of Life Sciences in Poznań. Scientific Dissertations 397. They dissolve in water, forming colloidal solutions. This is due to the large size of protein molecules and their specific solvation interactions with water molecules, thanks to which each protein molecule in the solution is surrounded by the so-called "Water jacket" (solvation shell). Solvation is possible here due to the presence of highly polar hydroxyl, carboxyl and amino groups in the amino acid side chains. Proteins can react with inorganic acids or salts and with carboxylic acids. In a slightly alkaline environment, they form salts due to the presence of -NH-CO- peptide bonds in their backbone polymer chains. Hence, for example, boric-protein systems in which boric acid forms salts with some of the -NH- groups can bind boron to the wood substance by gelling the protein. Likewise, condensation reactions with amide groups present in the protein mediate the fixation of carboxylic acids in wood. Therefore, when considering the structure of proteins in the aspect of wood saturation, four levels of their spatial arrangement should be considered. Changes occurring in the processes of heating impregnated wood or its secondary impregnation with an agent that changes the pH of the reaction environment, e.g. with tannic acid, resulting in the denaturation of the proteins contained in it, breaking the bonds stabilizing the secondary structure, i.e. second, third, fourth row, changing biological, chemical and physical properties of proteins. They become less soluble, and therefore, after forming salts with impregnants, they reduce the hygroscopicity of the lignocellulosic material. The reactivity of basic wood components with protein solutions of biologically active substances and their potential use in wood impregnation have been presented in the publications of Mazela B., Bartkowiak M., Ratajczak I. (2007): Animal protein impact on fungicidal properties of treatment formulations. Wood Research 52 (1): 13-22, Mazela B., Domagalski P., Mamonova M., Ratajczak I. (2007): Protein impact on the capability of the protein-borate preservative penetration and distribution into pine and aspen wood. Holz ais Roh- und Werkstoff 65: 137-144, Ratajczak I., Mazela B. (2007): The boron fixation to the cellulose, lignin and wood matrixthrough its reaction with protein. Holz ais Roh- und Werkstoff 65: 231-237, Ratajczak I., Hoffmann SK, Goslar J., Mazela B. (2008): Fixation of copper (ll) -protein formulation in wood: Part 1. Influence oftannic acid on fixation of copper in wood. Holzforschung 62 (3): 294-299, Hoffmann SK, Goslar J., Ratajczak I., Mazela B. (2008): Fixation of copper-protein formulation in wood: Part 2. Molecular mechanism of fixation of copper (ll) in cellulose, lignin and wood studied by EPR. Holzforschung 62 (3): 300-308, Mazela B. (2008): Prospects for increasing the durability of wood in terms of environmental protection requirements. Publishing house of the University of Life Sciences in Poznań. Scientific Dissertations 397.

The following types of protein (in the form of 5 to 50% aqueous solutions) can be used for the production of this insulation material:

a. Animal in the form of spray-dried plasma of red blood cells or in the form of albumin or casein. These proteins differ in their protein content due to the different concentration methods before drying and therefore the different anticoagulant residue in the form of sodium polyphosphates.

PL 230 478 Β1

They contain: spray-dried serum of animal blood plasma, serum globulins of blood plasma, lactose, citric acid, potassium chloride, lecithin, dl-methionine. Protein preparations from blood plasma, freeze-dried or obtained by ultrafiltration, are produced from stabilized animal blood and are characterized by very good emulsifying and gelling properties. An example is hemoglobin hydrolyzate used as a source of amino acids and peptides in crops under stress. It is characterized by good solubility in water. It consists of short-chain peptides and about 20% free amino acids. It shows good adhesive properties. Other animal proteins are e.g. egg white albumin or casein.

b. Vegetable - Protein of plant origin is poorer in terms of amino acid composition and does not contain one or more essential amino acids. Acidic hydrolyzate of soy protein was used in the research. Its higher hydrophilicity, compared to animal proteins, made it easier to prepare impregnating solutions. Biopolymer films and coatings based on soy protein are characterized by lower water resistance and higher water vapor permeability. Natural fillers such as proteins are used to reinforce polymer composites because they have many desirable characteristics that are harder to find with inorganic fillers. They show, among others: mechanical resistance, low density, good strength, thermal resistance, biodegradability, they are available and cheap.

Natural fillers such as proteins are used to reinforce polymer composites because they have many desirable characteristics that are harder to find with inorganic fillers. They show, among others: mechanical resistance, low density, good strength, thermal resistance, biodegradability, they are available and cheap.

3. Graphite - expanding graphite is a product of natural origin, it is produced from graphite ore in the process of enrichment, refining, and then treating pure graphite with strong oxidants and transforming it into dry graphitic acid. During this process, the graphite crystal lattice is intercalated with atoms of another element. Reheating the modified graphite leads to the release of the intercalant, breaking the interplanar bonds and exfoliation of the graphite crystals, resulting in the formation of nanoaggregations of graphene. As a result of this transformation, resulting from heating and exfoliation, graphite undergoes a strong volumetric expansion and turns into a soft, elastic and insulating material called expanded or elastic graphite. This material inherits many important features of flake graphite, has high thermal and chemical resistance, is self-lubricating, shields thermal and ultraviolet radiation. It is not subject to aging processes and environmental influences. EG (expandable graphite) graphite is used as an agent increasing fire resistance for various types of insulation, materials and coatings (flame retardant, flame retardant). Graphite EG, with a distinct flake structure and stronger protective properties, is intended as an additive to bituminous coverings, fireproofing and refractory coatings. Graphite adds up to 20% of the total mass of the material, depending on the type of application. Ground graphite EG with a powder consistency is intended as an additive to polymers, elastomers, foams, to be used directly as an admixture in the amount of 2-6%, or to be used in a liquid form. The addition of EG graphite reduces the flammability of the material by combining the effects of several phenomena. In the initial phase, graphite increases the thermal conductivity of the material and has a shielding effect on thermal radiation and does not allow the temperature to increase excessively, then the graphite swells and creates an insulating layer. Finally, the expanded graphite forms a tight membrane that protects against oxygen and flame penetration into the deeper layers of the material. Modified EG graphite has a number of advantages over traditional flame retardants, including:

a.high efficiency and higher oxygen index with comparable addition of other flame retardant,

b.high resistance and chemical inertness as well as no risk of interaction with the material,

c. as a mineral of natural origin, it is ecological, harmless and physiologically neutral, d. reacts quickly to heat or fire, it expands already at 150-200 ° C,

e. does not contain halogen and corrosive compounds, does not emit dioxins and furans while burning,

f. does not lose its properties over a long period of time or under the influence of external factors,

g. shows high thermal resistance (even at a temperature> 2500 ° C).

The action of graphite consists in, inter alia, hindering the access of oxygen to the flame zone and the formation of non-flammable decomposition products. A more effective solution is the use of expanding graphite, which additionally "swells" under the influence of temperature, creating a charred layer

PL 230 478 Β1 on burning material. Han Z., Dung L, Li Y., Zhao H .: Journal of Fire Sciences 2007, 25 (1), 79) reported that expandable graphite is used together with ammonium polyphosphate to reduce the flammability of polyethylene. In turn, the authors of another work Chen X., Yu J., Guo S., Luo Z., He M .: Journal of Macromolecular Science, Part A: Pure and Applied Chemistry 2008, 45, 712 based on the analysis of the oxygen index, UL tests -94 and thermogravimetric analysis showed the reduction of flammability of polypropylene composites containing in its composition expanding graphite together with magnesium hydroxide. Expandable graphite can also be used as a polyurethane flame retardant Thirumal M., Manjunath B.S., Nacik Y.P., Khastgir D., Smgha N.K .: Journal of Applied Polymer Science 2008, 110 (5), 2586. The authors of the work - XiangCheng B., Zhong-Ming L, Jian-Hua T .: Journal of Applied Polymer Science 2008, 110 (6), 3871 - to reduce the flammability of polyurethanes, they used expanding graphite and silicone compounds, showing their synergistic effect. Expandable graphite is also used as a flame retardant together with halogen compounds, e.g., decarbomodiphenylethane, as discussed in Ling Y., Jian-Hua T., Zhong-ming L., Xian-Yan M., Xing-Mao L .: Journal of Applied Polymer Science 2009, 111 (5), 2372). However, the use of halogen compounds is not pro-ecological. The authors of another publication used the composition of expanding graphite with polymethyl methacrylate Ye L., Meng Χ.Υ., Li Z., M., Tang JH: Polymer Degradation and Stability 2009, 94, 971 as a flame retardant additive for polyurethane foams. it showed not only lower flammability but also favorable mechanical properties. The authors of the work - Quan H., Zhang B., Zhao Q., Yuen R.K.K., Li R.K.Y .: Composites: Part A 2009, 40, 1506 obtained a polyurethane nanocomposite with reduced flammability thanks to the use of the nanometric structure of graphite. Expanding graphite used as an additive to reduce the flammability of plastics works synergistically with halogen-free flame retardants such as silicone compounds, hydrotalcite, ammonium polyphosphate Meng Χ.Υ., Tang JH: Journal of applied polymer science 2009, 15 (114), 853, Du L., Zhang Y., Yuan X, Chen J .: Polymer-Plastics Technology and Ecgineering 2009. Graphite is also used as a flame retardant additive for polystyrene. The authors of the work - Xiao M., Sun L., Liu J., Li Y., Gong K .: Polymer 2002, 43, 2245 - have increased the thermal stability of the material by obtaining a graphite-styrene nanocomposite. The currently known solutions using graphite and its modified variants to reduce the flammability of plastics are insufficient for many practical applications. It particularly concerned expanded polystyrene, where graphite acts as an additive increasing the insulating parameters of the material, not reducing its flammability. The authors of publications on graphite-polystyrene composites in most cases emphasize their favorable properties related to electrical conductivity and thermal insulation Goyal R.K., Mulik U.P., Jagadale P.A .: Journal of applied polymer science 2009, 111 (4), 2071.

4. Antibiocorrosive additives are active substances that are potential active ingredients protecting lignocellulosic particles against possible biological corrosion, they can be the following chemical compounds in the pure form or in the form of ready-made commercial preparations: boric acid, propionic acid, ethylbutyl acid, tannic acid, isothiazolone derivatives.

a. Boric acid is a known biologically active substance in the group of wood preservatives, which was discussed in the publication of Mazela B. (2008): Prospects for increasing the durability of wood in terms of environmental protection requirements. Publishing house of the University of Life Sciences in Poznań. Scientific Dissertations 397.

Boric acid (e.g., orthoboric acid, trioxoboric acid) is an inorganic chemical compound, a weak acid with the formula H3BO3. It occurs in nature as the mineral of sassolin. The salts of boric acid are borates (orthoborates). Boric acid is used as a fertilizer, as well as a disinfectant and insecticide. It is also used as a preservative. On the E-list of legal food additives in the European Union it is marked with the symbol (E-284). The optimal concentration in an aqueous solution is 5%. The effectiveness of boron compounds in the protection of wood has been known for many years, which were presented in the publications of Lutomski K., Neyman S.S. (1976): Preliminary results of investigations on screening test of Chemical compounds suitable forthe preservation of lignocellulosic materials against biodeterioration. IRG / WP 262, Lloyd J. D., Dickinson D. J., Murhy R. J. (1990): The probable mechanism of action of boric acid and borates as wood preservatives. IRG / WP 1450, TroyaDE M.T., Navarette A.M. (1991): Laboratory screening to determine the preventive effectiveness against blue stain fungi and molds. IRG / WP 3677, Drysdale J. A. (1994): Boroń treatments forthe preservation of wood -A review of efficacy data for fungi and termites. IRG / WP 94-30037, KartalS.N., Shinoda K., Imamura Y. (2005): Laboratory evaluation of boron-containing didecyl dimethyl ammonium tetrafluoroborate (DBF) for inhibition of mold and stain fungi. Holz a. Roh- u. Werkst. 63: 73-77, Kartal S.N., Hwang W.J.,

PL 230 478 Β1

Shinoda K., Imamura Y. (2006): Laboratory evaluation of boron-containing quaternary ammonia compound, didecyl dimethyl ammonium tetrafluoroborate (DBF) for control of decay and termite attack and fungal staining of wood. Holz A. Roh. Werkst. 64: 62-67. They are one of the few active substances with high efficiency and, at the same time, low toxicity towards higher organisms (Kartal et al. 2005, 2006). In the light of the Act on biocides, there are no restrictions on the use of boron compounds in the protection of wood so far, therefore, in practice, they are of paramount importance.

b. Propionic acid (e.g., ethane carboxylic acid) is an aliphatic carboxylic acid with the formula CH3CH2COOH. At room temperature, it is a colorless, water-soluble liquid with an unpleasant pungent odor. It is obtained by the oxidation of propyl alcohol. It is used in the production of fragrance esters and cellulose solvents. It occurs in milk and is produced in the digestive tract of animals. In the food industry, it is used as a food preservative (E-280). It is added to sliced packaged bread and rye bread and to pastry products in an amount of up to 3000 mg / kg. It is also added to animal feed as an anti-mold agent. This compound is included in the list of biologically active substances. Although it is not one of the active substances classified as wood preservatives, its effectiveness against wood-decomposing fungi was recognized in the course of studies in which it was used due to the ease of salt formation with proteins as a result of binding the carboxyl group to the amine group, presented in Ophardt 2003C. E. (2003): Virtual Chembook, Elmhurst College), Mazela B. (2008): Prospects for increasing the durability of wood in terms of environmental protection requirements. Publishing house of the University of Life Sciences in Poznań. Scientific Dissertations 397.).

c. 2-Ethylbutanoic acid (e.g., diethylacetic acid) is a saturated four-carbon carboxylic acid with the formula (C2H5) 2CHCOOH. It is a transparent liquid with a suffocating odor. It is found in rancid butter, animal fat and vegetable oils. It dissolves in water, ethanol and ether. It is obtained, among others by fermentation of sugar with calcium carbonate or by oxidation of butanol in the presence of potassium permanganate. As a strong acid, it reacts with bases, strong oxidants and metals. Its esters are used in the production of plastics, plasticizers and surfactants. They are also used as flavor and aroma additives for food, as well as in pharmaceutical and disinfectant preparations.

d. Tannin is a light yellow, yellowish or light brown, amorphous, odorless or sometimes faint odor and tangy powder. It is an organic compound. It is a combination of many gallic acid molecules (i.e. 3,4,5-trihydroxybenzoic acid) with a D-glucose molecule. Tannin occurs in nature, incl. in the tea leaf - Folium Theae and in galls - Cecidum. This compound belongs to the group known as tannins. It is also possible to obtain tannin synthetically. It combines with most heavy metal salts and precipitates many alkaloids from solutions. Tannin is used in addition to medicine, among others in the tanning industry, in the chemical industry, for the synthesis of dyes, and also as a mortar in dyeing. Tannin acid has a strong denaturing effect. It binds with proteins and creates water-insoluble bonds with them. It also denatures bacterial proteins, thanks to which it has a disinfecting effect.

e. Thiazole derivatives are known biologically active compounds found in the group of in-cane products. Due to the possible occurrence of microbial corrosion caused by fungi and / or bacteria, the active substance in the form of 1,2-benzisothiazolin-3 (2H) -one (CAS: 2634-33-5) in the amount of 0.008-0.06% to inhibit the possible growth of microorganisms.

The essence of the invention is a method for the production of a wood-based composite, consisting in that the previously processed and shredded shavings to the size of the fraction of 4-40 mm are soaked for at least 2 hours in a 5-50% protein solution, then the shavings are filtered, and then wet shavings soaked in protein, expanding graphite is added in a weight ratio of 9: 1, then the shavings with graphite are thoroughly mixed until good adhesion is obtained, and the surface of the shavings is evenly covered with graphite, then the whole is seasoned for 48 hours in order to pre-dry, then dry shavings is subjected to chamber drying at a temperature of at least 60 ° C, then the composite is packaged.

Preferably the protein preparation is a 20% animal derived protein solution in the form of a spray dried plasma of red blood cells, or albumin or casein.

It is also preferred that the protein preparation is a 20% aqueous solution of vegetable soy protein.

PL 230 478 Β1

It is also preferred that 5% of the antibiocorrosive agent of boric acid or propionic acid or ethylbutyl acid or tannic acid or an isothiazolone derivative is added to the composite.

It is particularly preferred that 5% of the flame retardant of a potassium carbonate solution or ammonium phosphate or 10% of water glass are added to the composite.

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

- the composite is an ecological material,

- protection of natural resources,

- environmental friendliness during production;

- even, almost closed CO2 balance (plants absorb as much CO2 from the atmosphere as they grow when removing waste from these materials),

- Energy saving,

- no emission of harmful substances to the atmosphere during use, during waste disposal and material processing, easy waste removal,

- short transport route (regional materials),

- the composite shows very good thermal and humidity properties, good acoustic protection,

- the composite is vapor-permeable, has a good thermal capacity and can transport moisture in the material without reducing power,

- the possibility of obtaining a stable microclimate of the interior of structural elements of building walls.

The following examples illustrate the invention:

Example I.

A 20% aqueous solution of hemoglobin was prepared in the form of a spray-dried plasma of red blood cells (animal protein) in which wood shavings, previously ground to a size of 40 mm, were soaked for 3 hours. After draining the chips from the hemoglobin solution, expanding graphite was added in portions to the chips in a weight ratio of 9: 1. The chips with graphite were thoroughly mixed to ensure good adhesion, and thus even coverage of the chip surface with graphite. The mixed chips with the deposited graphite are aged for 48 hours to pre-dry the composite. The initially dried chips were subjected to chamber drying at the temperature of 60 ° C. The composite prepared in this way was subjected to further known technological treatment.

After drying, the chips were subjected to flammability tests to determine the effectiveness of fire protection. The evaluation of the effectiveness was made on the basis of measurements of the weight loss and the exhaust gas temperature. The tests were carried out in triplicate. The research showed a very high efficiency (K = 9.39) with an average bulk density of 125.29 kg / m ³ .

Example II

A 20% aqueous solution of albumin (animal protein) was prepared, to which was added an antibiotic agent in the form of boric acid in the amount of 5% and a flame retardant solution of potassium carbonate in the amount of 5%, in which wood shavings, previously ground to a size of 10 mm, were soaked for 4 hours. . After draining the chips from the albumin solution, expanding graphite was added in portions to the chips in a weight ratio of 9: 1. The chips with graphite were thoroughly mixed to ensure good adhesion, and thus even coverage of the chip surface with graphite. The mixed chips with graphite deposited on their surface are seasoned for 48 hours in order to pre-dry the composite. The initially dried chips were subjected to chamber drying at the temperature of 90 ° C. The composite prepared in this way was subjected to further known technological treatment.

After drying, the chips were subjected to flammability tests to determine the effectiveness of fire protection. The evaluation of the effectiveness was made on the basis of measurements of the weight loss and the exhaust gas temperature. The tests were carried out in triplicate. The research showed high efficiency (K = 7.72) with an average bulk density of 101.52 kg / m ³ .

Example III

A 20% aqueous solution of casein (animal protein) was prepared, to which an antimicorrosive agent in the form of propionic acid was added in the amount of 5%, in which wood shavings, previously ground to a size of 20 mm, were soaked for 3 hours. After draining the chips from the solution, expanding graphite was added in portions to the chips in a weight ratio of 9: 1. Chips together with graphite exactly

PL 230 478 Β1 was mixed to ensure good adhesion and thus even coverage of the chip surface with graphite. The mixed chips with the deposited graphite were left for 48 hours to pre-dry the composite. The initially dried chips were subjected to chamber drying at the temperature of 90 ° C. The composite prepared in this way was subjected to further known technological treatment.

After drying, the wood chips were subjected to flammability tests in order to determine the effectiveness of the protection on the basis of weight loss and flue gas temperature. The tests were carried out in triplicate. Palnościowe tests have shown a very high efficiency (9.54) with an average bulk density of 134.45 kg / m ^3.

Example IV

A 20% aqueous solution of soy protein (vegetable protein) was prepared, to which a 5% propionic acid antimicrobial agent was added, in which wood shavings, previously ground to a size of 30 mm, were soaked for 3 hours. After draining the chips from the solution, expanding graphite was added in portions to the wet chips in a weight ratio of 9: 1. The chips with graphite were thoroughly mixed to ensure good adhesion, and thus even coverage of the chip surface with graphite. The mixed chips with the deposited graphite are aged for 48 hours to pre-dry the composite. The initially dried chips were subjected to chamber drying at the temperature of 90 ° C. The composite prepared in this way was subjected to further known technological treatment.

After drying, the wood chips were subjected to flammability tests in order to determine the effectiveness of the protection on the basis of weight loss and flue gas temperature. The tests were carried out in triplicate. Palnościowe tests have shown a very high efficiency (9.54) with an average bulk density of 134.45 kg / m ^3.

Example V

A 20% aqueous solution of soybean protein (vegetable origin) was prepared, to which an antimicrobial agent in the form of ethylbutylic acid was added in an amount of 5%, in which wood chips previously ground to a size of 40 mm were soaked for 3 hours. After draining the chips from the solution, expanding graphite was added in portions to the chips in a weight ratio of 9: 1. The chips with graphite were thoroughly mixed to ensure good adhesion, and thus even coverage of the chip surface with graphite. The mixed chips with the deposited graphite were left for 48 hours to pre-dry the composite. The initially dried chips were subjected to chamber drying at the temperature of 90 ° C. The composite prepared in this way was subjected to further known technological treatment.

After drying, the wood chips were subjected to flammability tests in order to determine the effectiveness of the protection on the basis of weight loss and flue gas temperature. The tests were carried out in triplicate. Palnościowe tests have shown a very high efficiency (9.54) with an average bulk density of 134.45 kg / m ^3.

Example VI

A 20% aqueous solution of plant-derived protein was prepared, to which an antimicrobial agent in the form of propionic acid was added in the amount of 5%, in which wood shavings, previously ground to a size of 40 mm, were soaked for 3 hours. After draining the chips from the solution, expanding graphite was added in portions to the chips in a weight ratio of 9: 1. The chips with graphite were thoroughly mixed to ensure good adhesion, and thus even coverage of the chip surface with graphite. The mixed chips with the deposited graphite were left for 48 hours to pre-dry the composite. The initially dried chips were subjected to chamber drying at the temperature of 90 ° C. The composite prepared in this way was subjected to further known technological treatment.

After drying, the wood chips were subjected to flammability tests in order to determine the effectiveness of the protection on the basis of weight loss and flue gas temperature. The tests were carried out in triplicate. Palnościowe tests have shown a very high efficiency (9.54) with an average bulk density of 134.45 kg / m ^3.

Example VII

A 20% aqueous solution of vegetable soybean protein was prepared, to which was added an antimicrobial agent, isothiazolone derivatives in the amount of 5%, in which wood shavings, previously ground to a size of 4-40 mm, were soaked for 3 hours. After draining the chips from the solution, expanding graphite was added in portions to the chips in a weight ratio of 9: 1. Chips with graphite to

PL 230 478 Β1 was thoroughly mixed to ensure good adhesion and thus even coverage of the chip surface with graphite. The mixed chips with the deposited graphite are aged for 48 hours to pre-dry the composite. The initially dried chips were subjected to chamber drying at the temperature of 90 ° C. The composite prepared in this way was subjected to further known technological treatment.

After drying, the wood chips were subjected to flammability tests in order to determine the effectiveness of the protection on the basis of weight loss and flue gas temperature. The tests were carried out in triplicate. Palnościowe tests have shown a very high efficiency (9.54) with an average bulk density of 134.45 kg / m ^3.

Example VIII

A 20% aqueous solution of vegetable soybean protein was prepared, to which an antibiocorrosive agent in the form of tannin acid in the amount of 5% and additionally a flame retardant in the form of potassium carbonate in the amount of 5% were added, in which shavings, previously ground to a size of 40 mm, were soaked for 3 hours. woody. After draining the chips from the solution, expanding graphite was added in portions to the chips in a weight ratio of 9: 1. The chips with graphite were thoroughly mixed to ensure good adhesion, and thus even coverage of the chip surface with graphite. The mixed chips with the deposited graphite were left for 48 hours to pre-dry the composite. The initially dried chips were subjected to chamber drying at the temperature of 90 ° C. The composite prepared in this way was subjected to further known technological treatment.

After drying, the wood chips were subjected to flammability tests in order to determine the effectiveness of the protection on the basis of weight loss and flue gas temperature. The tests were carried out in triplicate. Palnościowe tests have shown a very high efficiency (9.54) with an average bulk density of 134.45 kg / m ^3.

Example IX

A 20% aqueous solution of plant-derived protein was prepared, to which an antibiocorrosive agent in the form of propionic acid in the amount of 5% and additionally a flame retardant in the form of ammonium phosphate in the amount of 5% were added, in which wood shavings, previously crushed to a size of 40 mm, were soaked for 3 hours. . After the solution was filtered off, the expanding graphite was added in portions in a weight ratio of 9: 1. The chips with graphite were thoroughly mixed to ensure good adhesion, and thus even coverage of the chip surface with graphite. The mixed chips with the deposited graphite were left for 48 hours to pre-dry the composite. The initially dried chips were subjected to chamber drying at the temperature of 90 ° C. The composite prepared in this way was subjected to further known technological treatment.

After drying, the wood chips were subjected to flammability tests in order to determine the effectiveness of the protection on the basis of weight loss and flue gas temperature. The tests were carried out in triplicate. Palnościowe tests have shown a very high efficiency (9.54) with an average bulk density of 134.45 kg / m ^3.

Example X

A 20% aqueous solution of plant-derived protein was prepared, to which an antibiocorrosive agent in the form of propionic acid in the amount of 5% and an additional flame retardant in the form of water glass in the amount of 10% were added, in which, for 3 hours, previously crushed wood shavings were soaked to a size of 20 mm. . After the albumin solution was filtered off, expanding graphite was added in portions in a weight ratio of 9: 1 to the chips. The chips with graphite were thoroughly mixed to ensure good adhesion, and thus even coverage of the chip surface with graphite. The mixed chips with the deposited graphite were left for 48 hours to pre-dry the composite. The initially dried chips were subjected to chamber drying at the temperature of 90 ° C. The composite prepared in this way was subjected to further known technological treatment.

After drying, the wood chips were subjected to flammability tests in order to determine the effectiveness of the protection on the basis of weight loss and flue gas temperature. The tests were carried out in triplicate. Palnościowe tests have shown a very high efficiency (9.54) with an average bulk density of 134.45 kg / m ^3.

Example XI

A 20% aqueous solution of vegetable soy protein was prepared, to which was added an isothiazolone derivative antibiotic agent in the amount of 0.5% and additionally anti-burn agent.

PL 230 478 Β1 in the form of water glass in the amount of 10%, in which wood shavings, previously crushed to a size of 40 mm, were soaked for 3 hours. After the albumin solution was filtered off, expanding graphite was added in portions in a weight ratio of 9: 1 to the chips. The chips with graphite were thoroughly mixed to ensure good adhesion, and thus even coverage of the chip surface with graphite. The mixed chips with the deposited graphite were left for 48 hours to pre-dry the composite. The initially dried chips were subjected to chamber drying at the temperature of 90 ° C. The initially dried chips were subjected to chamber drying at the temperature of 90 ° C. The composite prepared in this way was subjected to further known technological treatment. The composite prepared in this way is subjected to further known technological treatment.

After drying, the chips were subjected to flammability tests in order to determine the effectiveness of the protection on the basis of the loss of mass and temperature of the exhaust gases. The tests were carried out in triplicate. Palnościowe tests have shown a very high efficiency (9.54) with an average bulk density of 134.45 kg / m ^3.

Application example

The task of the composite consisting of wood shavings and flame-retardant additives is thermal insulation of the building partition. Each building material, and in particular the insulation material, must have an equivalent moisture content at the time of incorporation into the building. In the case of an increase in humidity above the equivalent, the value of the heat transfer coefficient increases, i.e. deterioration of thermal insulation properties and an increase in susceptibility to the phenomenon of biological corrosion. For this reason, materials with a moisture content exceeding the equivalent moisture should not be incorporated. An important stage preceding the placement of the composite in the building partition is to ensure its adequate low humidity, i.e. not exceeding the level of 9%. Wood shavings saturated with flame retardant, after draining from the impregnating solution, are subjected to chamber drying in order to improve the technological process and ensure adequate humidity. In the next stage, the dried, loose insulation material is compacted in a known manner, placing it in a building partition, the building partition being kept in a room with constant relative humidity and air temperature in order to equalize the humidity of all its components. Such action minimizes the risk of biological corrosion and the risk of moisture deformation of other wooden structural elements.

The test of the effectiveness of fire protection of wood chips was carried out according to the modified Metz method, burning the prepared composite tests according to variants (I-III) and control tests (i.e. from non-impregnated chips) in a tube furnace. The modification of the method consisted in the production of a special basket made of steel mesh with a perforation 2x2 mm, diameter 5 cm and length 50 cm. Before the samples were burned, the tube furnace was tared in the form of a balance. The device was reset after the empty basket was suspended in the tubular furnace. An empty basket was weighed before the start of the tests. Samples of the tested composite were sprinkled in portions in a basket, successively compacting the loose material. After the basket was full, the batch was weighed to calculate the bulk density. Then, the basket with the composite sample was suspended in the pipe, and the scale of the apparatus was set in such a way that the deflected pointer showed a reading corresponding to 0.0% weight loss. A burner was placed under the suspended sample, which before the measurement was adjusted so that the gas flow was 4.5 l / min., The flame height was about 25 cm. The duration of exposure to the sample by the flame was 3 minutes. The weight loss (%) and the exhaust gas temperature at the outlet of the pipe were recorded at intervals of 0.5 minutes. Further observations and data logs were carried out for at least 3 min. from the moment the burner was turned off to the last three results of weight loss with the same value (for some tests, eg Option I, the duration was much shorter). Average values of the loss of mass depending on the time were plotted on the coordinate system.

The mean final value of the weight loss of the samples was used as the basis for the evaluation. The security performance was assessed on the basis of the following formula:

W = 10x (1 -E / A) where:

W - contractual effectiveness of the impregnation,

E - final weight loss for samples tested in%,

A - final weight loss for control samples in%.

The protection is considered to be good (i.e. effective) when W = 7.5, which corresponds to a weight loss of 20.5% and an area of 6.4 cm ^2, and the sample itself is extinguished 1 minute after the source of fire is cut off. Medium protection (i.e. operation still effective) when W = 5.5 + 7.5 which corresponds to

PL 230 478 Β1 weight loss of 37% and an area of 11.5 cm ² , and the extinguishing itself takes place in the period of 1-3 minutes, after removing the source of fire.

Parameters influencing thermal insulation - size and bulk density

Depending on the density and type of wood-based material (including loose material - chips) and the degree of its moisture content, the thermal conductivity coefficient varies significantly. For porous fibreboards with a density of 300 kg / m ^3, the thermal conductivity coefficient X (W / m * K) ranges from 0.06 for moderately humid conditions to 0.07 for humid conditions. On the other hand, for hard fibreboards with a density of 1000 kg / m ^3, this coefficient is 0.18 to 0.21, respectively. For bulk materials such as wood chips in bulk (250 kg / m ³⁾ bulk wood shavings (150 kg / m ^3), wood shavings compacted (300 kg / m ³⁾ ratio is suitably 0,09-0,12 (W / m * K), 0.09-0.12 (W / m * K), 0.07-0.08 (W / m * K). The main factor influencing the achievement of the appropriate thermal conductivity coefficient is the density of the material from which the insulation is made. Changing the dimensions of chips / shavings, and the degree of their compaction, affects the increase in the density of the insulation layer and its thermal conductivity. The used protein polymer in the form of animal or vegetable protein as a carrier of flame retardants has a positive effect on the insulating properties of the composite according to the invention. The thermal conductivity coefficient for concrete is on average 1.7 and for protein 0.57 (W / m * K). It follows that the obtained composite has good insulating properties than the material used so far. In addition, the hygroscopicity of the material is important. With increasing humidity, the thermal conductivity increases and therefore the insulating capacity decreases. Wood in the form of chips impregnated with a protein solution and then dried in the form of a loose composite (containing a flame retardant) shows reduced hygroscopicity. The reason for this are changes in the chemical structure resulting from the protein denaturation process (destruction of hydrogen bonds, breakage of disulfide bridges), which from then on is characterized by reduced water solubility, thus imparting hydrophobic properties to the surface of lignocellulosic particles. Bearing in mind not only the possibility of obtaining the appropriate bulk density of the insulating material, but also the possibility of easy impregnation of lignocellulosic particles and their mixing with a fire retardant in order to obtain a homogeneous composite, the chip extraction technology with the possibility of producing at least two fractions is important due to the application: a) , large area fraction for external walls and roofs; b). fine fraction for partition walls and ceilings.

The task of the composite consisting of wood shavings and flame-retardant additives is thermal insulation of the building partition. Each building material, and in particular the insulation material, must have an equivalent moisture content at the time of incorporation into the building. In the case of an increase in humidity above the equivalent, the value of the heat transfer coefficient increases, i.e. deterioration of thermal insulation properties and an increase in susceptibility to the phenomenon of biological corrosion. Table 1 shows the results of determining the effectiveness of fire protection.

Table 1

Variant average effectiveness average weight loss [%] average bulk density [kg / m ^3] soaking time [h] comments Control 94.00 71.30 strongly smokes Option I 9.39 6.00 125.29 3 unpleasant smell Option II 7.72 21.33 101.52 3 Option II 9.54 4.00 134.45 3 Cement 2.70 68.33 128.34 very long burning time with flashover stages fumes heavily

Claims (15)

Patent claims The method of producing wood-based composites, characterized in that the previously processed and crushed shavings to a fraction size of 4-40 mm are soaked for at least 2 hours in a 5-50% protein solution, then the shavings are filtered off, further to the wet shavings soaked in protein, expanding graphite is added in a weight ratio of 9: 1, then the chips with graphite are thoroughly mixed until good adhesion is obtained, the surface of the chips is evenly covered with graphite, then the whole is seasoned for 48 hours in order to pre-dry, then the dried chips are subjected to chamber drying at a temperature of at least 60 ° C, then the composite is packaged. 2. The method according to p. The method of claim 1, wherein the protein preparation is a 20% animal derived protein solution in the form of a spray-dried red blood cell plasma. 3. The method according to p. The process of claim 1, wherein the protein preparation is a 20% solution of an animal-derived protein albumin. 4. The method according to p. The process of claim 1, wherein the protein preparation is a 20% solution of animal-derived casein protein. 5. The method according to p. The process of claim 1, wherein the protein preparation is a 20% aqueous solution of vegetable soy protein. 6. The method according to p. The method of claim 1, wherein 5% of the antibiocorrosive agent is added to the composite. 7. The method according to p. 6. The process of claim 6, wherein the anti-corrosive agent is boric acid. 8. The method according to p. The process of claim 6, wherein the anti-biocorrosive agent is propionic acid. 9. The method according to p. The process of claim 6, wherein the anti-biocorrosive agent is ethylbutyl acid. 10. The method according to p. 6. The process of claim 6, wherein the anti-biocorrosive agent is tannic acid. 11. The method according to p. The process of claim 6, characterized in that the antibiotic agents are isothiazolone derivatives. 12. The method according to p. The method of claim 1, characterized in that 5% of the flame retardant is added to the composite. 13. The method according to p. The process of claim 1 or 12, characterized in that the flame retardant is a potassium carbonate solution. 14. The method according to p. The process of claim 1 or 12, characterized in that the flame retardant is ammonium phosphate. 15. The method according to p. The process of claim 1 or 12, characterized in that the flame retardant is 10% water glass.