A polymerizable triazolium salt for wood modification and a preparation method and application thereof

Abstract

The application relates to a polymerizable triazolium salt for wood modification and a preparation method and application thereof, and belongs to the field of wood mildewproof and antibacterial. The application aims at solving the problem that existing 1,2,4-triazole compounds cannot simultaneously have the biological activities of resisting mildew, resisting blue-stain fungi and resisting bacteria. The polymerizable triazolium salt for wood modification has the structural formula of the polymerizable triazolium salt is prepared by the following steps: dissolving a triazole compound in a polar solvent, adding a quaternary ammonium reagent after temperature is increased, cooling after reaction, removing the solvent, washing and vacuum drying, so that the polymerizable triazolium salt is obtained; and the application is used as a bactericide and can resist mildew, blue-stain fungi and bacterial infection.

Description

Technical Field

[0001] This invention belongs to the field of wood anti-mildew and antibacterial. Background Technology

[0002] Wood, as one of the most sustainable resources, is widely used in construction, decoration, flooring, and furniture. However, the micron-sized porous structure and abundant hydroxyl groups of wood make it highly hygroscopic, susceptible to decay, mold, and blue stain. It also easily attracts bacteria, forming biofilms on the wood surface. Studies have found that the amount of preservatives needed for wood preservation is generally much lower than that needed for mold and blue stain prevention. Mold and blue stain not only affect the usability and decorative function of wood but also threaten human health and quality of life. Long-term exposure to or inhalation of mold and its spores can cause allergic reactions, respiratory inflammation, skin or mucous membrane diseases, and in severe cases, even poisoning and death. The bacterial biofilms formed on the wood surface also significantly increase the risk of chronic bacterial infections in humans, and some bacteria can degrade wood and break down cell wall structures. Therefore, wood modification treatments are necessary to give it resistance to mold, blue stain fungi, and bacterial infections.

[0003] 1,2,4-Triazole compounds are widely used in wood protection, but they are biodegradable. For example, tebuconazole can be biodegraded by Gram-negative bacteria, specifically *Pseudomonas fluorescens*, and the triazole ring structure, the bactericidal active group, is preferentially cleaved. This means that 1,2,4-triazole compounds do not possess significant antibacterial activity. Summary of the Invention

[0004] This invention aims to address the problem that existing 1,2,4-triazole compounds cannot simultaneously possess antifungal, antiblue staining, and antibacterial bioactivity, and thus provides a polymerizable triazole salt for wood modification, its preparation method, and its application.

[0005] A polymerizable triazolium salt for wood modification, the structural formula of which is:

[0006] Where R1 is R2 is an alkyl group with a carbon chain length of 1 to 12; X is Cl, Br or I.

[0007] A method for preparing polymerizable triazolium salts for wood modification, comprising the following steps:

[0008] Triazole compounds were dissolved in a polar solvent, and the temperature was raised to 30℃~80℃. Then, a quaternizing agent was added, and the reaction was carried out at a constant temperature of 30℃~80℃ for 10h~40h. After the reaction, the mixture was naturally cooled to room temperature, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was washed with a weakly polar reagent and finally dried under vacuum to obtain polymerizable triazoleonium salts.

[0009] The molar ratio of the triazole compound to the quaternizing agent is 1:(0.5-4).

[0010] An application of a polymerizable triazolium salt for wood modification, which acts as a fungicide while resisting mold, blue stain and bacterial infections.

[0011] The beneficial effects of this invention are:

[0012] The polymerizable triazole onion salt compound of this invention possesses broad-spectrum and highly efficient bactericidal properties and is a novel quaternary ammonium salt compound. This invention utilizes commercially available triazole fungicides, leveraging the reactivity of the triazole ring, to prepare the compound via a one-step reaction with a terminal double-bond halogenated olefin. The reactants are widely available, the synthesis process is simple, and large-scale production is feasible. Using a lower alcohol as a solvent, the polymerizable triazole onion salt compound is uniformly distributed within the wood cell wall through atmospheric pressure impregnation. The modified wood exhibits certain control efficacy against Aspergillus niger and blue stain fungi, and significantly inhibits the growth and reproduction of Staphylococcus aureus and Escherichia coli on the wood surface. The modified wood simultaneously resists mold, blue stain fungi, and bacterial infections, enriching the application scenarios of wood products and increasing their added value. Furthermore, the prepared triazole onion salt compound contains an active C=C group in its structure, exhibiting polymerization activity, and can be chemically bonded to finishing materials such as acrylates, showing broad application prospects.

[0013] Instruction manual illustrations

[0014] Figure 1 The carbon NMR spectra of the polymerizable triazolium salts prepared in Examples 1 to 3 are shown below.

[0015] Figure 2 The carbon NMR spectra of the polymerizable triazolium salts prepared in Examples 4 to 6 are shown.

[0016] Figure 3 This is a graph showing the relationship between the drug loading of triazolyl salt-modified wood and the concentration of the modification solution in Example 7;

[0017] Figure 4The diagram shows the cross-sectional microstructure of the triazolium salt-modified wood in Example 7 and the distribution of bromine in the modified wood. (a1) and (a2) are compound 1, (b1) and (b2) are compound 2, (c1) and (c2) are compound 3, (d1) and (d2) are compound 4, (e1) and (e2) are compound 5, and (f1) and (f2) are compound 6.

[0018] Figure 5 The efficacy of triazolyl salt-modified wood in Example 7 against Aspergillus niger;

[0019] Figure 6 The efficacy of triazoline-modified wood in Example 7 against Diplococcus thecogene;

[0020] Figure 7 The antibacterial activity value of the triazodium salt-modified wood against Staphylococcus aureus in Example 7;

[0021] Figure 8 The antibacterial activity value of the triazodium salt-modified wood against Escherichia coli in Example 7;

[0022] Figure 9 The efficacy of modified wood treated with different triazolam salts and water washing in controlling Diplococcus thecogenes was investigated. Detailed Implementation

[0023] Specific Implementation Method 1: This implementation method provides a polymerizable triazoleonium salt for wood modification. The structural formula of the polymerizable triazoleonium salt is as follows:

[0024] Where R1 is R2 is an alkyl group with a carbon chain length of 1 to 12; X is Cl, Br or I.

[0025] The beneficial effects of this embodiment are:

[0026] The polymerizable triazole onion salt compound of this embodiment possesses broad-spectrum and highly effective bactericidal properties and is a novel quaternary ammonium salt compound. This embodiment utilizes a commercially available triazole bactericide. Based on the reactivity of the triazole ring, the compound is prepared through a one-step reaction with a terminal double-bond halogenated olefin. The reactants are widely available, the synthesis process is simple, and large-scale production is feasible. Using a lower alcohol as a solvent, the polymerizable triazole onion salt compound is uniformly distributed within the wood cell wall through atmospheric pressure impregnation. The modified wood exhibits certain control efficacy against Aspergillus niger and blue stain fungi, and significantly inhibits the growth and reproduction of Staphylococcus aureus and Escherichia coli on the wood surface. The modified wood simultaneously resists mold, blue stain fungi, and bacterial infections, enriching the application scenarios of wood products and increasing their added value. Furthermore, the prepared triazole onion salt compound contains an active C=C group in its structure, exhibiting polymerization activity, and can be chemically bonded to finishing materials such as acrylates, showing broad application prospects.

[0027] Specific Implementation Method Two: This implementation method provides a method for preparing polymerizable triazolium salts for wood modification, which is carried out according to the following steps:

[0028] Triazole compounds were dissolved in a polar solvent, and the temperature was raised to 30℃~80℃. Then, a quaternizing agent was added, and the reaction was carried out at a constant temperature of 30℃~80℃ for 10h~40h. After the reaction, the mixture was naturally cooled to room temperature, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was washed with a weakly polar reagent and finally dried under vacuum to obtain polymerizable triazoleonium salts.

[0029] The molar ratio of the triazole compound to the quaternizing agent is 1:(0.5-4).

[0030] Specific Implementation Method 3: This implementation method differs from Specific Implementation Method 2 in that the triazole compound is tebuconazole, propiconazole, triazole, hexaconazole, tebuconazole, or flusilazole. Everything else is the same as in Specific Implementation Method 2.

[0031] Specific Implementation Method Four: This implementation method differs from Specific Implementation Method Two or Three in that the polar solvent is ethanol, n-propanol, isopropanol, or acetonitrile. Everything else is the same as in Specific Implementation Method Two or Three.

[0032] Specific Implementation Method Five: This implementation method differs from Specific Implementation Methods Two to Four in that the quaternizing agent is a haloalkene with a terminal double bond. Everything else is the same as in Specific Implementation Methods Two to Four.

[0033] Specific Implementation Method Six: This implementation method differs from Specific Implementation Methods Two to Five in that the structural formula of the haloolefin with terminal double bonds is as follows:

[0034] Furthermore, in the structural formula of the haloalkene with terminal double bonds, X is Cl, Br, or I. Other aspects are the same as in specific embodiments two to five.

[0035] Specific Implementation Method Seven: This implementation method differs from Specific Implementation Methods Two to Six in that the weakly polar reagent is diethyl ether, acetone, ethyl acetate, or methyl tert-butyl ether. Everything else is the same as in Specific Implementation Methods Two to Six.

[0036] Specific Embodiment Eight: This embodiment differs from Specific Embodiments Two to Seven in that the mass ratio of the triazole compound to the volume of the polar solvent is 1 g:(4-10) mL. Everything else is the same as in Specific Embodiments Two to Seven.

[0037] Specific Implementation Method Nine: This implementation method describes the application of a polymerizable triazolium salt for wood modification, which acts as a fungicide while resisting mold, blue stain fungus, and bacterial infections.

[0038] Specific Implementation Method Ten: This implementation method differs from Specific Implementation Method Nine in that it is used as a bactericide, and is carried out specifically according to the following steps:

[0039] Polymerizable triazonium salts are dissolved in a solvent to obtain a modified solution. Wood is then immersed in the modified solution until its wet weight is stable. It is then removed and air-dried naturally. Finally, the solvent is removed by drying to obtain triazonium salt-modified wood.

[0040] The modified solution contains 0.5% to 2.5% by mass of polymerizable triazolium salt; the solvent is ethanol, n-propanol, or isopropanol. Other aspects are the same as in Specific Embodiment Nine.

[0041] The beneficial effects of the present invention are verified using the following embodiments:

[0042] Example 1:

[0043] A method for preparing polymerizable triazolium salts for wood modification, comprising the following steps:

[0044] 3.07 g of tebuconazole (0.01 mol) was dissolved in 15 mL of acetonitrile, the temperature was raised to 50 °C, and then 3.62 g of 3-bromo-1-propene (0.03 mol) was added. The reaction was carried out at a constant temperature of 50 °C for 10 h. After the reaction, the mixture was allowed to cool naturally to room temperature. The solvent was removed by rotary evaporation to obtain the crude product. The crude product was washed with methyl tert-butyl ether and finally dried under vacuum at room temperature to obtain the polymerizable triazolium salt.

[0045] The washing of the crude product with methyl tert-butyl ether is carried out in the following steps: ① Add 60 mL of methyl tert-butyl ether to the crude product and stir for 0.5 h at a speed of 300 ppm. After stirring, centrifuge to obtain a solid product; ② Repeat step ① washing the solid product 3 times.

[0046] This embodiment contains a polymerizable triazolium salt, whose structural formula is:

[0047] In this embodiment, the polymerizable triazolium salt is labeled as compound 1, with a yield of 92.7%.

[0048] Example 2:

[0049] A method for preparing polymerizable triazolium salts for wood modification, comprising the following steps:

[0050] 3.07 g of tebuconazole (0.01 mol) was dissolved in 15 mL of acetonitrile, the temperature was raised to 80 °C, and then 4.47 g of 5-bromo-1-pentene (0.03 mol) was added. The reaction was carried out at 80 °C for 20 h. After the reaction, the mixture was allowed to cool naturally to room temperature. The solvent was removed by rotary evaporation to obtain the crude product. The crude product was washed with methyl tert-butyl ether and finally dried under vacuum at room temperature to obtain the polymerizable triazolium salt.

[0051] The washing of the crude product with methyl tert-butyl ether is carried out in the following steps: ① Add 60 mL of methyl tert-butyl ether to the crude product and stir for 0.5 h at a speed of 300 ppm. After stirring, centrifuge to obtain a solid product; ② Repeat step ① washing the solid product 3 times.

[0052] This embodiment contains a polymerizable triazolium salt, whose structural formula is:

[0053] In this embodiment, the polymerizable triazolium salt is labeled as compound 2, with a yield of 56.6%.

[0054] Example 3:

[0055] A method for preparing polymerizable triazolium salts for wood modification, comprising the following steps:

[0056] 3.07 g of tebuconazole (0.01 mol) was dissolved in 15 mL of acetonitrile, the temperature was raised to 80 °C, and then 6.57 g of 10-bromo-1-decene (0.03 mol) was added. The reaction was carried out at 80 °C for 30 h. After the reaction, the mixture was allowed to cool naturally to room temperature. The solvent was removed by rotary evaporation to obtain the crude product. The crude product was washed with methyl tert-butyl ether and finally dried under vacuum at room temperature to obtain a polymerizable triazolium salt.

[0057] The washing of the crude product with methyl tert-butyl ether is carried out in the following steps: ① Add 60 mL of methyl tert-butyl ether at 4 °C to the crude product and stir for 0.5 h at a speed of 300 ppm. After stirring, centrifuge to obtain a solid product; ② Repeat step ① washing the solid product 3 times.

[0058] This embodiment contains a polymerizable triazolium salt, whose structural formula is:

[0059] In this embodiment, the polymerizable triazolium salt is labeled as compound 3, with a yield of 50.3%.

[0060] Example 4:

[0061] A method for preparing polymerizable triazolium salts for wood modification, comprising the following steps:

[0062] 3.42 g of propiconazole (0.01 mol) was dissolved in 15 mL of acetonitrile, the temperature was raised to 50 °C, and then 3.62 g of 3-bromo-1-propene (0.03 mol) was added. The reaction was carried out at a constant temperature of 50 °C for 10 h. After the reaction, the mixture was allowed to cool naturally to room temperature. The solvent was removed by rotary evaporation to obtain the crude product. The crude product was washed with methyl tert-butyl ether and finally dried under vacuum at room temperature to obtain a polymerizable triazolium salt.

[0063] The washing of the crude product with methyl tert-butyl ether is carried out in the following steps: ① Add 60 mL of methyl tert-butyl ether to the crude product and stir for 0.5 h at a speed of 300 ppm. After stirring, centrifuge to obtain a solid product; ② Repeat step ① washing the solid product 3 times.

[0064] This embodiment contains a polymerizable triazolium salt, whose structural formula is:

[0065] In this embodiment, the polymerizable triazolium salt is labeled as compound 4, with a yield of 82.0%.

[0066] Example 5:

[0067] A method for preparing polymerizable triazolium salts for wood modification, comprising the following steps:

[0068] 3.42 g of propiconazole (0.01 mol) was dissolved in 15 mL of acetonitrile, the temperature was raised to 80 °C, and then 4.47 g of 5-bromo-1-pentene (0.03 mol) was added. The reaction was carried out at 80 °C for 20 h. After the reaction, the mixture was naturally cooled to room temperature, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was washed with methyl tert-butyl ether and finally dried under vacuum at room temperature to obtain the polymerizable triazolium salt.

[0069] The washing of the crude product with methyl tert-butyl ether is carried out in the following steps: ① Add 60 mL of methyl tert-butyl ether at 4 °C to the crude product and stir for 0.5 h at a speed of 300 ppm. After stirring, centrifuge to obtain a solid product; ② Repeat step ① washing the solid product 3 times.

[0070] This embodiment contains a polymerizable triazolium salt, whose structural formula is:

[0071] In this embodiment, the polymerizable triazolium salt is labeled as compound 5, with a yield of 46.1%.

[0072] Example 6:

[0073] A method for preparing polymerizable triazolium salts for wood modification, comprising the following steps:

[0074] 3.42 g of propiconazole (0.01 mol) was dissolved in 15 mL of acetonitrile, the temperature was raised to 80 °C, and then 6.57 g of 10-bromo-1-decene (0.03 mol) was added. The reaction was carried out at 80 °C for 30 h. After the reaction, the mixture was allowed to cool to room temperature naturally. The solvent was removed by rotary evaporation to obtain the crude product. The crude product was washed with methyl tert-butyl ether and finally dried under vacuum at room temperature to obtain a polymerizable triazolium salt.

[0075] The washing of the crude product with methyl tert-butyl ether is carried out in the following steps: ① Add 60 mL of methyl tert-butyl ether at -20℃ to the crude product and place it in a refrigerator at -20℃ overnight, then filter to obtain a filter cake; ② Wash the filter cake three times with methyl tert-butyl ether at -20℃ as described in step ①.

[0076] This embodiment contains a polymerizable triazolium salt, whose structural formula is:

[0077] In this embodiment, the polymerizable triazolium salt is labeled as compound 6, with a yield of 40.7%.

[0078] Figure 1 The carbon NMR spectra of the polymerizable triazolium salts prepared in Examples 1 to 3 are shown below. Figure 2The figures show the carbon NMR spectra of the polymerizable triazole onion salts prepared in Examples 4 to 6. As can be seen from the figures, by performing a simple quaternization reaction on the triazole fungicide, the triazole compound is transformed into a brominated triazole onion salt. The synthesized triazole onion salts all contain terminal double bond groups in their structure and have certain polymerization activity.

[0079] Example 7:

[0080] An application of polymerizable triazolium salts for wood modification:

[0081] The polymerizable triazolium salts prepared in Examples 1 to 6 were dissolved in solvents to obtain modified solutions. Wood was immersed in the modified solutions until its wet weight stabilized, then removed and air-dried naturally. Finally, it was dried at 103°C to remove the solvent, resulting in triazolium salt-modified wood. The mass percentage of polymerizable triazolium salt in the modified solutions was 0.5%, 1.0%, 1.5%, 2.0%, and 2.5%. The solvent was n-propanol.

[0082] The wood used was eucalyptus. Specimens were sawn to two dimensions: 50mm (longitudinal) × 20mm (tangential) × 1.8mm (radial) and 30mm (longitudinal) × 30mm (tangential) × 1.8mm (radial). They were dried at 40℃ to constant weight. The length, width, and thickness of the specimens were measured and recorded to an accuracy of 0.1mm. The mass before and after impregnation was recorded (the mass before impregnation is the mass after drying at 40℃, and the mass after impregnation is the wet weight) to calculate the drug loading. For tests of anti-mildew and anti-blue stain performance and surface antibacterial performance, 6 and 3 parallel specimens were set up, respectively.

[0083] Figure 3 This is a graph showing the relationship between the drug loading of triazonium salt-modified wood and the concentration of the modifying solution in Example 7. The graph shows that the drug loading of the modified eucalyptus wood is directly proportional to the concentration of the impregnation solution. When the impregnation solution concentration is 2.5%, the drug loading of the modified eucalyptus wood is 6.97 ± 1.34 kg / m³. 3 6.98±1.22kg / m 3 6.93±1.30kg / m 3 7.14±1.30kg / m 3 7.10±1.15kg / m 3 7.12±0.65kg / m 3 .

[0084] Figure 4The diagram shows the cross-sectional microstructure of the triazolium salt-modified wood in Example 7 and the distribution of bromine in the modified wood. (a1) and (a2) represent compound 1, (b1) and (b2) represent compound 2, (c1) and (c2) represent compound 3, (d1) and (d2) represent compound 4, (e1) and (e2) represent compound 5, and (f1) and (f2) represent compound 6. As can be seen from the diagram, there is no obvious separation of cells in the modified eucalyptus wood, the cell structure is intact, and the triazolium salt is evenly distributed in the cell wall of the modified eucalyptus wood.

[0085] (1) Anti-mildew and anti-discoloration performance test: The experiment was conducted in accordance with the "Test Method for the Control Efficacy of Anti-mildew Agents against Wood Molds and Discoloration Fungi" (GB / T18261-2013). After the triazodium salt-modified wood was exposed to mold and blue stain fungi environment for four weeks, the surface infection value was recorded and the control efficacy was calculated.

[0086] The criteria for evaluating the surface contamination value of the specimens are shown in Table 1 below.

[0087] Table 1 Evaluation Criteria for Anti-mold, Anti-discoloration, and Anti-infection Values

[0088]

[0089] The efficacy of prevention and treatment is calculated using the following formula.

[0090]

[0091] In the formula: E—prevention and control efficacy, %;

[0092] D1—The average infection value of the sample treated with the agent;

[0093] D0—The average infection value of the untreated control sample.

[0094] Figure 5 The efficacy of triazolyl salt-modified wood in Example 7 against Aspergillus niger; Figure 6 This study examines the control efficacy of triazophos-modified wood against *Thecoccus dispora* in Example 7. The control efficacy of triazophos-modified eucalyptus against *Aspergillus niger* and *Thecoccus dispora* is positively correlated with concentration. When the concentration of the modification solution is 2.5%, the control efficacy of the modified eucalyptus against *Aspergillus niger* is less than 75%. At the same treatment concentration, the modified eucalyptus exhibits higher control efficacy against *Thecoccus dispora*, with compounds 1 and 3 achieving 100% control efficacy. Modified eucalyptus impregnated with tebuconazole quaternized products shows overall higher fungal control efficacy and better fungal control performance.

[0095] (2) Antibacterial performance test: The experiment was conducted in accordance with the standard "Test of Antibacterial Activity and Efficacy of Antibacterial Products" (DISZ2801). First, a 15 g / L nutrient broth culture medium solution was prepared, then diluted 500 times to obtain a 1 / 500 nutrient broth culture solution. This 1 / 500 nutrient broth culture solution was added to a slant culture medium test tube containing activated bacteria on the surface. The solution was repeatedly rinsed with a pipette to remove the bacterial growth. Then, it was transferred to an Erlenmeyer flask containing glass beads, shaken well, and then serially diluted 1:10 to maintain a bacterial concentration of 10%. 5 CFU / mL ~10 6 The inoculum concentration was determined to be CFU / mL. Before inoculation, the wood specimens were wrapped in multiple layers of gauze and sterilized by steam at 103℃ for 30 minutes. After cooling, inoculation was performed. The experiment included an experimental group and two control groups. Control group 1 measured the average number of viable cells on the surface of untreated wood specimens inoculated with the inoculum. Control group 2 measured the average number of viable cells 24 hours after inoculation. The specific procedures were as follows: Specimens from the same group were placed on freshly prepared nutrient agar medium to keep the surface moist. 0.1 mL of the inoculum was accurately transferred to the specimen surface using a pipette. For control group 1, the specimen surface was immediately rinsed with 9.9 mL of physiological saline after the inoculum was added, followed by a 1:10 dilution. Plate counting was performed on the inoculum at different dilutions. After inoculating the specimens of control group 2 and the experimental group with bacteria, the culture dishes were sealed and placed in a constant temperature incubator at 37℃ for 24 hours. Then, following the surface rinsing procedure of control group 1, the total number of colonies on the specimen surface was determined by plate counting method, and the antibacterial activity value was calculated.

[0096] The antibacterial activity value is calculated using the following formula:

[0097]

[0098] In the formula: R—antibacterial activity value;

[0099] A—The average number of viable cells directly obtained after inoculation of specimen 1 in the control group;

[0100] B—The average number of viable cells obtained from the control group 2 specimens after inoculation and 24 hours of storage;

[0101] The average number of viable cells obtained from C-triazolium salt-modified wood specimens after inoculation and 24 hours of storage.

[0102] The inhibition rate is calculated using the following formula:

[0103] Inhibition rate = (BC) / B (Equation 3)

[0104] B—The average number of viable cells obtained from the control group 2 specimens after inoculation and 24 hours of storage;

[0105] The average number of viable cells obtained from C-triazolium salt-modified wood specimens after inoculation and 24 hours of storage.

[0106] Figure 7 The antibacterial activity value of the triazodium salt-modified wood against Staphylococcus aureus in Example 7; Figure 8 The values ​​represent the antibacterial activity of triazodium salt-modified wood against *Escherichia coli* in Example 7. Triazodium salt-modified eucalyptus exhibits superior antibacterial activity against *Staphylococcus aureus* compared to *Escherichia coli*. Eucalyptus modified with compounds 1, 2, 3, and 5 showed antibacterial activity values ​​exceeding 3 against *Staphylococcus aureus* at a 2.5% concentration of the modified solution, with an inhibition rate exceeding 99.9%. Eucalyptus modified with compounds 1 and 3 showed antibacterial activity values ​​exceeding 1.5 against *Escherichia coli* at a 2.5% concentration of the modified solution, with an inhibition rate reaching 97%. Bacterial growth on the surface of triazodium salt-modified eucalyptus was significantly inhibited. Eucalyptus impregnated with tebuconazole quaternized products showed generally higher antibacterial activity values ​​and better bacterial control performance.

[0107] (3) Water washing loss experiment:

[0108] Wood treated with a polymerizable triazonium salt (2.5% by mass) as described in Example 7 was subjected to a water wash-loss experiment. The triazonium-modified wood was first conditioned to humidity equilibrium at 20°C and 65% humidity. Then, it was soaked in 120 mL of distilled water, with a weight pressing the specimen below the water surface. During the soaking process, the water was changed sequentially after 6 hours and 24 hours, and then every 48 hours for the remaining soaking time. After 7 days and 6 hours of soaking, the specimens were removed, air-dried, and dried at 103°C for later use, yielding water-washed modified eucalyptus wood. Six parallel groups of specimens were set up for the experiment. Because eucalyptus wood modified with compounds 1-6 has a higher control efficacy against *Thecoccus pluvialis*, the water-washed modified eucalyptus wood was exposed to a blue stain fungus environment for four weeks. The surface infection value was recorded, and the control efficacy was calculated, thus indirectly reflecting the anti-loss performance of compounds 1-6. The experiment was conducted in accordance with the "Test Method for the Control Efficacy of Antifungal Agents against Wood Molds and Discoloration Fungi" (GB / T18261-2013).

[0109] Figure 9 The efficacy of modified eucalyptus wood treated with different triazonium salts in two steps (impregnation and washing) against *Thecocococoa dispora* was investigated. As shown in the figure, modified eucalyptus wood still exhibited some efficacy against *Thecococoa dispora* after washing. Specifically, the efficacy of modified eucalyptus wood impregnated with compounds 1 and 2 after washing was 80%, slightly higher than the efficacy of modified eucalyptus wood (unwashed) prepared with an impregnation solution containing 2% of the corresponding compounds (by mass) against *Thecococoa dispora*. Figure 6This indicates that compounds 1 and 2 have good anti-leaking properties and can effectively protect wood from blue stain fungus infection even after water washing experiments.

Claims

1. An application of a polymerizable triazolium salt for wood modification, characterized in that... Polymerizable triazoline salts are used as bactericides to combat bacterial infections; the bacteria mentioned are Staphylococcus aureus and Escherichia coli. Furthermore, polymerizable triazolium salts can be used as fungicides, specifically by following these steps: Polymerizable triazonium salts are dissolved in a solvent to obtain a modified solution. Wood is then immersed in the modified solution until its wet weight is stable. It is then removed and air-dried naturally. Finally, the solvent is removed by drying to obtain triazonium salt-modified wood. The modified solution contains polymerizable triazolium salt at a mass percentage of 0.5% to 2.5%; the solvent is ethanol, n-propanol, or isopropanol. The structural formula of the polymerizable triazolium salt is as follows: ; Where R1 is , R2 is an alkyl group with a carbon chain length of 1 to 12; X is Cl, Br, or I. The polymerizable triazolium salt is prepared according to the following steps: Triazole compounds were dissolved in a polar solvent, and the temperature was raised to 30℃~80℃. Then, a quaternizing agent was added, and the reaction was carried out at a constant temperature of 30℃~80℃ for 10h~40h. After the reaction, the mixture was naturally cooled to room temperature, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was washed with a weakly polar reagent and finally dried under vacuum to obtain polymerizable triazoleonium salts. The molar ratio of the triazole compound to the quaternizing agent is 1:(0.5~4); The triazole compounds mentioned are tebuconazole, propiconazole, triazole, hexaconazole, tebuconazole, or flusilazole; The polar solvent is ethanol, n-propanol, isopropanol, or acetonitrile; The quaternizing agent is a haloalkene with a terminal double bond; The structural formula of the haloolefin with terminal double bonds is as follows: , , , , , , , , , , or And in the structural formula of the haloalkene with terminal double bonds, X is Cl, Br or I; The weakly polar reagent is diethyl ether, acetone, ethyl acetate, or methyl tert-butyl ether; The mass ratio of the triazole compound to the volume ratio of the polar solvent is 1 g:(4~10) mL.

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