RU2764926C1 - Wood modification method - Google Patents

Abstract

FIELD: woodworking industry.

SUBSTANCE: invention relates to the woodworking industry, in particular to the production of treated wood to increase its water resistance. Wood is processed by the immersion method in an impregnating solution under normal conditions, followed by heat treatment. In this case, 3% of the mass is used as the impregnating solution. a solution of a previously obtained copolymer of glycidyl methacrylate and hexyl methacrylate, decyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, stearyl methacrylate derivative of methacrylate in methyl ethyl ketone, with a molar ratio of monomers equal to (4-1.5):1. The impregnation is carried out for 2 hours, and the heat treatment is carried out at 140°C for 2 hours.

EFFECT: process of wood hydrophobization is simplified and its water resistance is increased.

1 cl, 4 dwg, 1 tbl

Description

The invention relates to a method for obtaining treated wood to improve its water resistance and can be used in all sectors of the economy where wood and wood products are used.

A known method of treating wood with tall oil (patent RU 2375169, IPC V27K3/00, V27K3/50, V27K3/34, 10.12.2009). The impregnating mixture is prepared as follows: tall oil is preheated to a temperature of 180-220°C, then air is supplied to it for 90-150 minutes, maintaining the above temperature, after which a dehydration catalyst is introduced in an amount of 0.5-3% by weight tall oil, then tall oil is kept at a temperature of 200-250°C for 2-5 hours, after which the wood is impregnated at a temperature of 130-170°C for 10-60 minutes and then subjected to heat treatment at a temperature of 155-185°C within 3-8 hours.

The disadvantage of this method is the use of high temperature for the preparation and further aging of tall oil, as well as the duration of the processing.

A method for producing modified wood is known (patent RU 2712521, IPC V27K5/06, 02/07/2019), including wood impregnation with a stabilizer, drying and pressing. The impregnation solution is prepared by adding 2-3% glacial 100% acetic acid to cardanol to obtain a pH of 6.3-6.5; % by dry residue, after that the blanks are dried under a mechanical pressure of 0.8 MPa and a temperature of 100-120°C to a moisture content of 6-8%, and after pressing, heat treatment is carried out at a temperature of 150-155°C for 8 hours.

The disadvantages of this method is the technological complexity of the process. It is also necessary to control the processing temperature and the availability of special press equipment to create pressure.

A known method of modifying wood (patent RU 2212335, IPC B27K3/44, 3/50, B05D7/06, 7/24, C09D5/14, 07/26/2002), a composition containing synthetic oligopiperylene rubber with a molecular weight of 15000-25000, dissolved in organic solvent - turpentine, and oil bitumen in the following ratio of components, wt.%: synthetic oligo-piperylene rubber - 8-40, oil bitumen - 15-50, turpentine - the rest.

The disadvantages of the method are the use of expensive synthetic oligopropylene rubber, the use of turpentine, which provides intensive penetration of the composition into the wood, but is a combustible, explosive material, as well as the use of bitumen, which significantly changes the color and texture of the material, which spoils the appearance of the wood.

A known method of hydrophobization using a composition (patent RU 2729741, IPC V27K3 / 34, 12/16/2019), including petroleum bitumen (BNI-4), used motor mineral oil obtained from base distillate oil, and technical paraffin. Impregnation is carried out in a hot bath at a wood moisture content of not more than 25% (GOST 20022.6-93). Samples of birch wood of the size required for water absorption tests were placed in the impregnating liquid, heated to a temperature of 115-125°C, and held for 40 minutes.

The disadvantages of this method include the high temperature of the impregnating liquid. The use of used mineral motor oil is not environmentally safe, as it is a toxic waste.

A known method for the manufacture of modified wood (SU 1306714, IPC B27K3 / 15, 5/06, 10.12.1985), where as a water-repellent additive to styrene, a polyethylhydrosiloxane liquid is used in an amount of 2-8 wt. hours per 100 wt. hours of styrene. Wood samples are evacuated at a residual pressure of 2-5 kPa for 20-30 minutes, then kept in an impregnating composition for 30-45 minutes. Polymerization is carried out at a temperature of 60±2°C for 6-8 hours, and heat treatment - at 95-100°C for 2-3 hours. After polymerization, physical and mechanical tests of the modified wood are carried out.

The disadvantage of this method is the duration of the technological process (average 12 hours).

The closest technical solution is a method for producing modified wood using the product of emulsion copolymerization of ethyl acrylate with styrene Emukril C or the product of copolymerization of acrylic monomers Emukril M (patent RU 2381895, IPC V27K3/00, V27K3/04, 20.02.2010). Impregnation is carried out at a temperature at a temperature of 18-22°C for 3 days, and heat treatment at a temperature of 80°C for 10 hours. 22, for 30 days - 81. For Emukril C, data on water absorption for 2 hours - 14 wt. %.

The disadvantage of this method is the duration of the impregnation and heat treatment processes, which is 82 hours.

The objective of the invention is to develop an effective method for producing modified wood with increased water resistance.

EFFECT: simplification of the method of wood hydrophobization and increase of its water resistance.

The technical result is achieved in a method for modifying wood, including the processing of wood by the immersion method in an impregnating solution under normal conditions, followed by heat treatment, while 3% of the mass is used as an impregnating solution. a solution of a preliminarily obtained copolymer of glycidyl methacrylate and a hexyl methacrylate, decyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, stearyl methacrylate of a methacrylate derivative selected from a series in methyl ethyl ketone, at a molar ratio of monomers equal to (4-1.5): 1, impregnation is carried out for 2 hours, and heat treatment is carried out at 140 ° C for 2 hours.

The essence of the method is the modification of wood, giving it hydrophobic properties. Modification is carried out by impregnation with a solution of a copolymer, which is used as 3% of the mass. a solution of a copolymer of glycidyl methacrylate and alkyl methacrylate (methacrylate derivative) in methyl ethyl ketone at a molar ratio of monomer units of glycidyl methacrylate: alkyl methacrylate equal to (4-1.5): 1. The alkyl methacrylate used was hexyl methacrylate, decyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, or stearyl methacrylate.

Wood is impregnated by the immersion method for 2 hours, and further heat treatment is carried out at 140°C for 2 hours.

To carry out the modification, a pre-dried sample of pine wood was placed in a container. To avoid floating, the sample was covered from above with a net, on top of which a weight was placed. 3% of the mass was poured into the container. solution of the copolymer in methyl ethyl ketone so that the sample is completely immersed and a solution layer of at least 5 mm remains above the wood sample. The impregnation was carried out for 2 hours. After the impregnation, the wood sample was removed from the modifier solution, subjected to heat treatment at 140°C for 2 hours. Then the dried sample was removed from the oven and left in air (under normal conditions) for 10 minutes to cooling and then weighed.

The main advantage of this impregnation method over others is that pre-synthesized polymers can be characterized by conventional chemical and physical methods. Also, this impregnation method is less complex from a chemical point of view and seems to be more technologically advanced.

As a result of two-hour impregnation, the average weight change lies in the range of 0.8-1.3 wt %, i.e. during modification, copolymers are chemisorbed into the surface layer and further heat treatment makes it possible to obtain covalently fixed polymer coatings. Impregnation of wood with a solution of the copolymer in methyl ethyl ketone does not change the appearance of the samples, they remain light.

The synthesized copolymers are characterized by low molecular weight along with a narrow molecular weight distribution.

The obtained polymer impregnating solutions based on glycidyl methacrylate and alkyl methacrylate have hydrophobic properties. The hydrophobic properties of polymeric impregnations of modified wood were evaluated by the wetting angle. The results of the study are presented in the table.

table

The table shows that as a result of the modification of pine wood samples, the wetting regime changes, the surface acquires highly and superhydrophobic properties with wetting angles up to 156°. There is a significant difference in contact angles on surfaces with different fiber orientations, which is associated with roughness. So on the surface across the fibers, the wetting angle exceeds the superhydrophobicity limit of 150°, and along the fibers, the values of the contact angles are mainly in the range of 133-147°.

The study of water absorption was carried out for wood modified with copolymers as a result of impregnation for 2 hours at room temperature and further heat treatment at a temperature of 140°C for 2 hours. The results are shown in the figures.

In FIG. 1 shows graphs of the dynamics of wood water absorption: without modifier - 1; after modification with the modifier glycidyl methacrylate : decyl methacrylate at molar ratios of monomer units: 2 - (1.5:1), 3 - (2:1), 4 - (2.5:1), 5 - (4:1).

In FIG. 2 shows graphs of the dynamics of wood water absorption: without modifier - 1; after modification with the modifier glycidyl methacrylate : lauryl methacrylate at molar ratios of monomer units: 2 - (1.5:1), 3 - (2:1), 4 - (2.5:1), 5 - (4:1).

In FIG. 3 shows graphs of wood water absorption dynamics: without modifier – 1; after modification with the modifier glycidyl methacrylate : tetradecyl methacrylate at molar ratios of monomer units: 2 - (1.5:1), 3 - (2:1), 4 - (2.5:1), 5 - (4:1).

In FIG. 4 shows graphs of the dynamics of wood water absorption: without modifier - 1; after modification with the modifier glycidyl methacrylate : stearyl methacrylate at molar ratios of monomeric units: 2 - (1.5:1), 3 - (2:1), 4 - (2.5:1), 5 - (4:1).

The study of water absorption of modified wood shows that the structure and composition of the polymer modifier significantly affect the properties. All modified samples are characterized by lower water absorption compared to the original wood. When modified by a number of copolymers, the water absorption index is significantly affected by the length of the hydrocarbon substituent of the functional comonomer. A noticeable decrease in water absorption is observed already at the initial stages of holding samples in water. So after 24 hours of stay of the samples in the input, the original wood gained 107 wt. %, and modified with a copolymer of glycidyl methacrylate with stearyl methacrylate, 64, 49, 48 and 42 wt. % according to the ratio of monomer units (glycidyl methacrylate : stearyl methacrylate = 4:1; 2.5:1; 2:1 and 1.5:1). An increased content of functional comonomer leads to a decrease in oxygen-containing groups in the near-surface layer, which ensures less water sorption. However, with prolonged contact with an aqueous medium, even for a ratio of glycidyl methacrylate : stearyl methacrylate = 1.5: 1, a significant increase in the weight of the samples is observed: 188 wt. % for the original, 132% for the modified after 30 days.

The penetrating power of the copolymer solutions used was determined as follows: a dye for organic solvents, which is not absorbed by wood, was added to the ready-made copolymer solutions. Next, the wood samples were placed in a glass without contact with each other. The top was covered with a net, on top of which a load was placed. The glasses were poured 3% of the mass. solutions of copolymers in methyl ethyl ketone so that the samples are completely immersed and a solution layer of at least 5 mm remains above the wood samples. The impregnation was carried out for 2 h. After the impregnation, the wood samples were removed from the modifier solutions, the surface of the samples was dried with filter paper, and weighed with an error of no more than 0.02 g. After that, the samples were split along the fibers in two directions perpendicular to each other and to the side surfaces. On the split surfaces, the depth of penetration of the modifying solution was determined. The penetration depth was determined by the colored zone and determined visually using a metal ruler with an error of no more than 0.5 mm. So, as a result of determining the penetrating ability, it was found that the penetration of copolymer solutions along the fibers of the samples is from 3 mm.

Synthesis of copolymers with molar ratios of glycidyl methacrylate:alkyl methacrylate equal to 4-1.5:1 was carried out in methyl ethyl ketone at 70°C for 24 hours. Azobisisobutyronitrile was used as the initiator. The polymer was precipitated into ice-cold methanol, filtered off on a Bunsen flask and dried under reduced pressure for 24 hours. For impregnation of wood prepared 3% of the mass. solutions of the obtained copolymers in methyl ethyl ketone.

Example 1 Synthesis of a copolymer of glycidyl methacrylate and stearyl methacrylate with a molar ratio of 4:1 was carried out in methyl ethyl ketone at 70°C for 24 hours. The initiator azobisisobutyronitrile (0.0081 g; 0.0492 mmol) was dissolved in 11.98 ml of methyl ethyl ketone, then purged with argon for 20 minutes and glycidyl methacrylate (1.61 ml, 11.8 mmol) and stearyl methacrylate (1.16 ml, 2.95 mmol). The resulting reaction mixture was kept at 70°C for 24 hours. The polymer was precipitated into ice-cold methanol, filtered off on a Bunsen flask, and dried under reduced pressure for 24 h.

To carry out the modification, a pre-dried sample of pine wood was placed in a container. To avoid floating, the sample was covered from above with a net, on top of which a weight was placed. 3% of the mass was poured into the container. copolymer solution in methyl ethyl ketone so that the sample is completely immersed and a solution layer of at least 5 mm remains above the wood sample. The impregnation was carried out for 2 hours. After the impregnation, the wood sample was removed from the modifier solution, subjected to heat treatment at 140°C for 2 hours. Then the dried sample was removed from the oven and left in air (under normal conditions) for 10 minutes to cooling and then weighed.

Example 2. The method is carried out analogously to example 1 with a molar ratio of glycidyl methacrylate and stearyl methacrylate monomers equal to 2.5:1. 8.16 ml of methyl ethyl ketone, 0.0057 g (0.0344 mmol) of azobisisobutyronitrile, 1.008 ml (7.38 mmol) of glycidyl methacrylate, 1.16 ml (2.95 mmol) of stearyl methacrylate were used.

Example 3. The method is carried out analogously to example 1 with a molar ratio of glycidyl methacrylate and stearyl methacrylate monomers equal to 2:1. 6.88 ml of methyl ethyl ketone, 0.0048 g (0.0295 mmol) of azobisisobutyronitrile, 0.806 ml (5.9 mmol) of glycidyl methacrylate, 1.16 ml (2.95 mmol) of stearyl methacrylate were used.

Example 4. The method is carried out analogously to example 1 at a molar ratio of glycidyl methacrylate and stearyl methacrylate monomers equal to 1.5:1. 5.61 ml of methyl ethyl ketone, 0.004 g (0.0246 mmol) of azobisisobutyronitrile, 0.605 ml (4.43 mmol) of glycidyl methacrylate, 1.16 ml (2.95 mmol) of stearyl methacrylate were used.

Examples 5, 9, 13, 17. The method is carried out analogously to example 1 with a molar ratio of monomers of glycidyl methacrylate and alkyl methacrylate, selected from the series tetradecyl methacrylate, lauryl methacrylate, decyl methacrylate, hexyl methacrylate, equal to 4:1.

Examples 6, 10, 14, 18. The method is carried out analogously to example 1 at a molar ratio of monomers of glycidyl methacrylate and alkyl methacrylate, selected from the series tetradecyl methacrylate, lauryl methacrylate, decyl methacrylate, hexyl methacrylate, equal to 2.5:1.

Examples 7, 11, 15, 19. The method is carried out analogously to example 1 at a molar ratio of monomers of glycidyl methacrylate and alkyl methacrylate, selected from the series tetradecyl methacrylate, lauryl methacrylate, decyl methacrylate, hexyl methacrylate, equal to 2:1.

Examples 8, 12, 16, 20. The method is carried out analogously to example 1 with a molar ratio of glycidyl methacrylate and alkyl methacrylate monomers selected from the series tetradecyl methacrylate, lauryl methacrylate, decyl methacrylate, hexyl methacrylate equal to 1.5:1.

Thus, a simplified method of wood modification, including the processing of wood by the immersion method for 2 hours under normal conditions in an impregnating solution - 3% of the mass. solution of a copolymer of glycidyl methacrylate and selected from a series of hexyl methacrylate, decyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, stearyl methacrylate of a methacrylate derivative in methyl ethyl ketone at a molar ratio of monomeric units of glycidyl methacrylate : alkyl methacrylate equal to (4-1.5): 1, subsequent heat treatment at 140 ° C for 2 hours provides hydrophobization of wood and increase of its water resistance.

Claims (1)

A method for modifying wood, including the processing of wood by the immersion method in an impregnating solution under normal conditions, followed by heat treatment, characterized in that 3% of the mass is used as an impregnating solution. a solution of a preliminarily obtained copolymer of glycidyl methacrylate and a hexyl methacrylate, decyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, stearyl methacrylate of a methacrylate derivative selected from a series in methyl ethyl ketone, at a molar ratio of monomers equal to (4-1.5): 1, impregnation is carried out for 2 hours, and heat treatment is carried out at 140 ° C for 2 hours.

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