Dry rot tree hole cleaning composition for ancient tree maintenance and application thereof

Abstract

The invention relates to the technical field of ancient tree maintenance and discloses a dry-rot tree hole cleaning composition for ancient tree maintenance and an application thereof. The key to repairing a tree hole is how to prevent the tree hole from further decaying. The prepared hydroxyl-containing quaternary ammonium salt long-chain siloxane has an antibacterial quaternary ammonium salt structure, and the hydrophobic quaternary ammonium salt is introduced into a hydrophilic polyurethane molecular chain, which is beneficial to the preparation of a polyurethane foaming agent and exhibits good antibacterial durability. In addition, the tree hole also needs to be waterproofed, and the introduction of silicon-oxygen bonds not only promotes good compatibility with polyurethane, but also improves the water resistance of the material. At the same time, the tree hole also needs to effectively isolate harmful insects, and pyrazole compounds have extremely high activity and high-efficiency and low-toxic insect resistance. In addition, the modified polyurethane is added to a foaming agent for foaming, which can completely fill the tree hole part, ensuring the normal growth of the ancient tree while improving its ornamental value.

Description

Technical Field

[0001] The present invention relates to the technical field of ancient tree maintenance, and in particular to a dry-rot tree hole cleaning composition for ancient tree maintenance and application thereof. Background Art

[0002] Ancient and famous trees are not just ornamental plants, they are also precious protected resources, have valuable medicinal research value, and play an extremely important role in maintaining ecological balance. However, due to human destruction of the living environment of some ancient trees or neglect of their care, the exposed wood of some ancient trees is washed and soaked by rainwater, gradually causing insects to rot, resulting in hollowness inside the trunks, and various tree holes are formed on the trunks, which not only affect the growth and development of the trees, but may also damage the ecological environment structure and reduce the ornamental value. Therefore, "first aid" for the damaged parts of ancient trees is of very important historical and cultural significance.

[0003] The hollows on the trunks of some ancient trees harbor dirt and grime, and need to be filled in time, otherwise the damaged areas will expand and spread, and even endanger the life of the trees. In recent years, scholars have done a lot of research on filling tree holes for the protection of ancient trees. Some commonly used repair techniques include cement and brick and stone repair methods, but cement mortar has poor bonding with tree tissue. Generally, after a few years of repair, the living cells around the tree hole mouth form a ring-shaped healing scab, which will push and squeeze the solidified cement blocks outward, creating gaps and thus destroying the overall shape of the ancient tree, affecting its normal growth. Patent No. CN100581347C discloses an application of polyurethane rigid foam in the rejuvenation and maintenance of ancient trees and famous trees. Steel bars and wire mesh are connected into an indefinite shape, which is placed in the tree hole as an internal support. The two liquids of foaming agent, isocyanate and polyether, are mixed and stirred in proportion and poured into the tree hole. The outside is fixed and closed with a prefabricated mold, and bark-like patterns are pressed on it or a layer of real bark is nailed on it. The prepared polyurethane rigid foam is waterproof and pressure-resistant, and its contraction and expansion properties are close to those of the tree itself. It can be tightly combined with the trunk and can effectively prevent the tree from being further damaged. However, the prepared polyurethane material does not conform to the growth law of the wood, resulting in cracks in the filled part, breeding pests and diseases, and further leading to the rot of the heartwood layer. On the basis of the existing material, the present invention utilizes the good shrinkage and ductility of polyurethane foam to modify the polyurethane. The modified polyurethane foam has the antibacterial properties of quaternary ammonium salt and the insect resistance of pyridine. It is filled into the tree hole, so that the ancient tree can be effectively prevented from being infected by pests and diseases, and the original tree hole can be effectively prevented from continuing to rot. Moreover, the modified polyurethane foam is not easily separated from the tree body and has a strong bonding strength with the wood, which is beneficial to the ventilation and growth of the ancient tree. Summary of the Invention

[0004] (1) Technical problems solved

[0005] In view of the deficiencies in the prior art, the present invention provides a dry-rot tree hole cleaning composition for ancient tree maintenance and its application, which solves the problem that ancient trees are prone to rot and form holes.

[0006] (2) Technical solution

[0007] The preparation method of the dry rot tree hole cleaning composition for ancient tree maintenance is as follows:

[0008] Step S1: Ethylene glycol diglycidyl ether and (N,N-dimethyl-3-aminopropyl)trimethoxysilane are added to anhydrous tetrahydrofuran solvent in sequence, and the mixture is stirred evenly. Glacial acetic acid is added at 20-35° C. to adjust the pH of the system to 3-4. After the reaction is completed, the mixture is concentrated and recrystallized from ethyl acetate to obtain a hydroxyl-containing quaternary ammonium salt-type long-chain siloxane.

[0009] Step S2, adding a quaternary ammonium salt-type long-chain siloxane containing a hydroxyl group and 1-methyl-3-phenyl-1H-pyrazole-5-carboxylic acid to an anhydrous toluene solvent in sequence, stirring evenly and then adding p-toluenesulfonic acid. After the reaction is completed, washing with petroleum ether, separating and concentrating the liquid to obtain a quaternary ammonium salt siloxane containing a pyrazole ring.

[0010] Step S3: Add polyether polyol, catalyst triethylenediamine and stannous octoate, and deionized water into the reaction bottle in sequence, stir evenly, then add toluene diisocyanate and quaternary ammonium siloxane containing a pyrazole ring, stir until the system turns white, and then transfer to a foaming box for foaming to obtain a dry rot tree hole cleaning composition for ancient tree maintenance.

[0011] Preferably, in step S1, the reactants are calculated by weight as follows: 100 parts of ethylene glycol diglycidyl ether and 210-260 parts of (N,N-dimethyl-3-aminopropyl)trimethoxysilane.

[0012] Preferably, the reaction temperature in step S1 is 80-100° C., and the reaction time is 24-48 hours.

[0013] Preferably, in step S2, the reactants are calculated by weight as follows: 100 parts of the hydroxyl-containing quaternary ammonium salt-type long-chain siloxane, 30-38 parts of 1-methyl-3-phenyl-1H-pyrazole-5-carboxylic acid, and 6-15 parts of p-toluenesulfonic acid.

[0014] Preferably, the reaction temperature in step S2 is 100-130° C., and the reaction time is 12-24 h.

[0015] Preferably, the components in step S3 are, by weight, 100 parts of polyether polyol, 0.6-1.0 parts of triethylenediamine, 0.2-0.5 parts of stannous octoate, 9-15 parts of deionized water, 30-50 parts of toluene diisocyanate, and 2-15 parts of quaternary ammonium salt siloxane containing a pyrazole ring.

[0016] (3) Beneficial technical effects

[0017] The invention first utilizes ethylene glycol diglycidyl ether and (N,N-dimethyl-3-aminopropyl)trimethoxysilane under the catalytic action of glacial acetic acid to prepare a quaternary ammonium salt long-chain siloxane containing a hydroxyl group, then reacts with pyridinic acid in the presence of p-toluenesulfonic acid to obtain a quaternary ammonium salt siloxane containing a pyridine ring, and finally obtains a dry rot tree hole cleaning composition for ancient tree maintenance under the action of polyether polyol, toluene diisocyanate, a catalyst and a foaming agent.

[0018] The key to repairing tree holes is how to prevent the wood in the hole from further decaying. The hydroxyl-containing quaternary ammonium salt long-chain siloxane first prepared by the present invention has an antibacterial quaternary ammonium salt structure, and the hydrophobic quaternary ammonium salt is introduced into the hydrophilic polyurethane molecular chain, which is conducive to the adsorption of the bactericide on the bacterial surface, maintaining the antibacterial performance and reflecting good antibacterial durability; in addition, the tree hole also needs to be waterproofed, and the introduction of silicon-oxygen bonds, taking advantage of the Si-O bond length, not only promotes good compatibility with polyurethane, but also improves the water resistance and aging resistance of the material; at the same time, the tree hole also needs to effectively isolate harmful insects, and pyrazole compounds have extremely high activity, high efficiency and low toxicity insect resistance and structural diversity; in addition, the polyurethane modified with quaternary ammonium salt and pyrazole is added with a foaming agent for foaming, so that it expands like bread and can completely fill the hole part, which is very effective for the situation where the inside of the hole is seriously uneven, not only preventing the filler from flowing out, but also preventing other external harmful substances from entering, ensuring the normal growth of the ancient tree while increasing its ornamental value. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a schematic diagram of the preparation of quaternary ammonium salt-type long-chain siloxane containing hydroxyl groups.

[0020] Figure 2 This is a schematic diagram of the preparation of quaternary ammonium siloxane containing a pyrazole ring. DETAILED DESCRIPTION

[0021] The present invention is further described below with reference to the following embodiments and accompanying drawings. It should be understood that the embodiments described herein are merely a portion of the present invention, and not all of the present invention. All other embodiments derived from the embodiments herein without creative effort by persons skilled in the art are intended to fall within the scope of protection of the present invention.

[0022] Example 1

[0023] Step S1, adding 100 parts by weight of ethylene glycol diglycidyl ether and 220 parts of (N,N-dimethyl-3-aminopropyl)trimethoxysilane to anhydrous tetrahydrofuran solvent in sequence, stirring evenly, adding glacial acetic acid at 25° C., adjusting the pH of the system to 4, reacting at 100° C. for 28 hours, concentrating, and recrystallizing from ethyl acetate to obtain a quaternary ammonium salt-type long-chain siloxane containing a hydroxyl group.

[0024] Step S2, adding 100 parts by weight of a hydroxyl-containing quaternary ammonium salt long-chain siloxane and 30 parts of 1-methyl-3-phenyl-1H-pyrazole-5-carboxylic acid to an anhydrous toluene solvent, stirring evenly, adding 10 parts of p-toluenesulfonic acid, reacting at 110° C. for 20 hours, washing with petroleum ether, separating and concentrating the liquid to obtain a quaternary ammonium salt siloxane containing a pyrazole ring.

[0025] Step S3: add 100 parts of polyether polyol, 0.6 parts of triethylenediamine, 0.5 parts of stannous octoate and 12 parts of deionized water in parts by weight into the reaction bottle in sequence, stir evenly, add 40 parts of toluene diisocyanate and 2 parts of quaternary ammonium siloxane containing a pyrazole ring, stir until the system turns white, and then transfer to a foaming box for foaming to obtain a dry rot tree hole cleaning composition for ancient tree maintenance.

[0026] Example 2

[0027] Step S1, adding 100 parts by weight of ethylene glycol diglycidyl ether and 260 parts of (N,N-dimethyl-3-aminopropyl)trimethoxysilane to anhydrous tetrahydrofuran solvent in sequence, stirring evenly, adding glacial acetic acid at 35° C., adjusting the pH of the system to 3, reacting at 80° C. for 24 hours, concentrating, and recrystallizing from ethyl acetate to obtain a hydroxyl-containing quaternary ammonium salt-type long-chain siloxane.

[0028] Step S2, adding 100 parts by weight of a hydroxyl-containing quaternary ammonium salt long-chain siloxane and 35 parts of 1-methyl-3-phenyl-1H-pyrazole-5-carboxylic acid to an anhydrous toluene solvent, stirring evenly, adding 10 parts of p-toluenesulfonic acid, reacting at 130° C. for 18 hours, washing with petroleum ether, separating and concentrating the liquid to obtain a quaternary ammonium salt siloxane containing a pyrazole ring.

[0029] Step S3: add 100 parts of polyether polyol, 0.8 parts of triethylenediamine, 0.25 parts of stannous octoate and 9 parts of deionized water in parts by weight into the reaction bottle in sequence, stir evenly, add 35 parts of toluene diisocyanate and 6 parts of quaternary ammonium siloxane containing a pyrazole ring, stir until the system turns white, and then transfer to a foaming box for foaming to obtain a dry rot tree hole cleaning composition for ancient tree maintenance.

[0030] Example 3

[0031] Step S1, adding 100 parts by weight of ethylene glycol diglycidyl ether and 230 parts of (N,N-dimethyl-3-aminopropyl)trimethoxysilane to anhydrous tetrahydrofuran solvent in sequence, stirring evenly, adding glacial acetic acid at 35° C., adjusting the pH of the system to 3, reacting at 100° C. for 32 hours, concentrating, and recrystallizing from ethyl acetate to obtain a hydroxyl-containing quaternary ammonium salt-type long-chain siloxane.

[0032] Step S2, adding 100 parts by weight of a hydroxyl-containing quaternary ammonium salt long-chain siloxane and 38 parts of 1-methyl-3-phenyl-1H-pyrazole-5-carboxylic acid to an anhydrous toluene solvent, stirring evenly, adding 14 parts of p-toluenesulfonic acid, reacting at 120° C. for 20 hours, washing with petroleum ether, separating and concentrating the liquid to obtain a quaternary ammonium salt siloxane containing a pyrazole ring.

[0033] Step S3: add 100 parts of polyether polyol, 0.8 parts of triethylenediamine, 0.4 parts of stannous octoate and 14 parts of deionized water in parts by weight into the reaction bottle in sequence, stir evenly, add 50 parts of toluene diisocyanate and 10 parts of quaternary ammonium siloxane containing a pyrazole ring, stir until the system turns white, and then transfer to a foaming box for foaming to obtain a dry rot tree hole cleaning composition for ancient tree maintenance.

[0034] Example 4

[0035] Step S1, adding 100 parts by weight of ethylene glycol diglycidyl ether and 250 parts of (N,N-dimethyl-3-aminopropyl)trimethoxysilane to anhydrous tetrahydrofuran solvent in sequence, stirring evenly, adding glacial acetic acid at 25° C., adjusting the pH of the system to 4, reacting at 90° C. for 48 hours, concentrating, and recrystallizing from ethyl acetate to obtain a hydroxyl-containing quaternary ammonium salt-type long-chain siloxane.

[0036] Step S2, adding 100 parts by weight of a hydroxyl-containing quaternary ammonium salt long-chain siloxane and 33 parts of 1-methyl-3-phenyl-1H-pyrazole-5-carboxylic acid to an anhydrous toluene solvent, stirring evenly, adding 15 parts of p-toluenesulfonic acid, reacting at 100° C. for 24 hours, washing with petroleum ether, separating and concentrating the liquid to obtain a quaternary ammonium salt siloxane containing a pyrazole ring.

[0037] Step S3: add 100 parts of polyether polyol, 1.0 part of triethylenediamine, 0.5 part of stannous octoate and 10 parts of deionized water in parts by weight into the reaction bottle in sequence, stir evenly, add 45 parts of toluene diisocyanate and 15 parts of quaternary ammonium siloxane containing a pyrazole ring, stir until the system turns white, and then transfer to a foaming box for foaming to obtain a dry rot tree hole cleaning composition for ancient tree maintenance.

[0038] Comparative Example 1

[0039] Step S1, adding 100 parts by weight of ethylene glycol diglycidyl ether and 220 parts of (N,N-dimethyl-3-aminopropyl)trimethoxysilane to anhydrous tetrahydrofuran solvent in sequence, stirring evenly, adding glacial acetic acid at 25° C., adjusting the pH of the system to 4, reacting at 100° C. for 28 hours, concentrating, and recrystallizing from ethyl acetate to obtain a quaternary ammonium salt-type long-chain siloxane containing a hydroxyl group.

[0040] Step S2: add 100 parts of polyether polyol, 1.0 part of triethylenediamine, 0.5 part of stannous octoate and 10 parts of deionized water in sequence to the reaction bottle, stir evenly, add 45 parts of toluene diisocyanate and 15 parts of hydroxyl-containing quaternary ammonium salt-type long-chain siloxane, stir until the system turns white, and then transfer to a foaming box for foaming to obtain a dry rot tree hole cleaning composition containing quaternary ammonium salt.

[0041] Comparative Example 2

[0042] Step S1: add 100 parts of polyether polyol, 2 parts of silicone foam leveling agent, 0.8 parts of triethylenediamine, 0.4 parts of stannous octoate and 14 parts of deionized water to the reaction bottle in sequence, stir evenly, then add 50 parts of toluene diisocyanate and 15 parts of 1-methyl-3-phenyl-1H-pyrazole-5-carboxylic acid, stir until the system turns white, and then transfer to a foaming box for foaming to obtain a dry rot tree hole cleaning composition containing pyrazole.

[0043] Antibacterial performance test: The antibacterial properties of the samples were tested by the shake flask method.

[0044] The polyurethane foam was cut into 2 cm × 2 cm samples, washed with ethanol and added to the activated solution at a concentration of 1 × 10 5 cfu / mL-5×10 5 cfu / mL of bacterial suspension, then place it on a shaking shaker at 300 r / min and shake for 5 minutes. Then take 2 mL of the bacterial suspension and dilute it to 100 times; take 1 mL of the shaken sample liquid and inoculate it on agar. Incubate it at 37°C under natural light for 48 hours.

[0045] Antibacterial rate (%) Diameter of inhibition zone (mm) Example 1 89.3 7.3 Example 2 95.1 8.5 Example 3 98.6 9.4 Example 4 99.8 10.6 Comparative Example 1 83.5 7.2 Comparative Example 2 65.4 6.3

[0046] As can be seen from the above table, with the increase of the quaternary ammonium salt content in the dry rot tree hole cleaning composition, the antibacterial rate against Escherichia coli gradually increases, reaching 99.8% in Example 4. Comparative Example 2 does not contain quaternary ammonium salt, but the antibacterial rate still reaches 65.4%. This is because the chemical structure of pyrazole substances belongs to phenol derivatives and has an antibacterial effect similar to phenol; the diameter of the inhibition zone also increases from 6.3 mm in Comparative Example 2 without quaternary ammonium salt to 10.6 mm, indicating that the prepared quaternary ammonium salt compound can adsorb negatively charged bacteria, causing structural damage to the cell wall, thereby having a strong antibacterial effect on bacteria.

[0047] Activity determination of diamondback moth: Use the immersion method. Prepare the test solution first, and use tweezers to immerse the olive leaves for 3-5 seconds. After the solution dries, put it into a marked 10 cm long straight tube, and insert 50 2nd-instar diamondback moths. Cover the tube with gauze. Test the results after 48 hours and calculate the mortality rate of the larvae.

[0048] Determination of rice planthopper activity: Using the rice bud immersion method, 10-12 cm long rice seedlings were immersed in the corresponding treatment solution. After immersion for 3-5 seconds, they were taken out and the rice planthopper larvae were spread out on newspaper to absorb the excess solution. The larvae were then implanted in 100 mL transparent breeding bottles and kept warm and moist for 48 hours. The mortality rate of the larvae was calculated.

[0049] Mortality rate = (number of dead insects / number of test insects) × 100%

[0050] Diamondback moth mortality rate (%) Rice planthopper mortality (%) Example 1 72 66 Example 2 78 70 Example 3 88 74 Example 4 96 86 Comparative Example 1 18 22 Comparative Example 2 78 60

[0051] As can be seen from the above table, with the increase of the pyrazole content in the polyurethane foam, the prepared dry-rot tree hole cleaning composition can achieve a maximum killing rate of 96% for diamondback moths and a killing rate of 86% for rice planthoppers, indicating that pyrazole-containing compounds have higher insect resistance and are more suitable for the promotion of insecticides; while the comparative example 1 which does not contain a pyrazole structure has a lower mortality rate for the two larvae, indicating that quaternary ammonium salts have certain insect resistance, but are far less than pyrazole compounds; therefore, introducing quaternary ammonium salts and pyrazole rings into the filling of the tree hole at the same time can not only prevent the tree hole from further decay, but also has an insect-resistant effect, thereby ensuring the normal growth of the ancient tree.

[0052] Based on the disclosure of the above description, those skilled in the art to which the present invention belongs may also make appropriate changes and modifications to the above embodiments. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and changes to the present invention should also fall within the scope of protection of the claims of the present invention. It should be pointed out that those skilled in the art may make several improvements and supplements without departing from the method of the present invention, and such improvements and supplements should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a composition for cleaning dry-rot tree holes for ancient tree maintenance, characterized in that: The preparation method is as follows: Step S1, adding ethylene glycol diglycidyl ether and (N,N-dimethyl-3-aminopropyl)trimethoxysilane to anhydrous tetrahydrofuran solvent in sequence, stirring evenly, adding glacial acetic acid at 20-35° C., adjusting the pH of the system to 3-4, concentrating after the reaction, and recrystallizing from ethyl acetate to obtain a quaternary ammonium salt-type long-chain siloxane containing a hydroxyl group; Step S2, adding a quaternary ammonium salt-type long-chain siloxane containing a hydroxyl group and 1-methyl-3-phenyl-1H-pyrazole-5-carboxylic acid to an anhydrous toluene solvent in sequence, stirring evenly, adding p-toluenesulfonic acid, washing with petroleum ether after completion of the reaction, separating and concentrating the liquid to obtain a quaternary ammonium salt siloxane containing a pyrazole ring; Step S3: Add polyether polyol, catalyst triethylenediamine and stannous octoate, and deionized water into the reaction bottle in sequence, stir evenly, then add toluene diisocyanate and quaternary ammonium siloxane containing a pyrazole ring, stir until the system turns white, and then transfer to a foaming box for foaming to obtain a dry rot tree hole cleaning composition for ancient tree maintenance.

2. The method for preparing the dry-rot tree hole cleaning composition for ancient tree maintenance according to claim 1, characterized in that: In step S1, the reactants are calculated by weight: 100 parts of ethylene glycol diglycidyl ether and 210-260 parts of (N,N-dimethyl-3-aminopropyl)trimethoxysilane.

3. The method for preparing the dry-rot tree hole cleaning composition for ancient tree maintenance according to claim 1, characterized in that: In step S1, the reaction temperature is 80-100° C., and the reaction time is 24-48 hours.

4. The method for preparing the dry-rot tree hole cleaning composition for ancient tree maintenance according to claim 1, characterized in that: In step S2, the reactants are calculated by weight as follows: 100 parts of the hydroxyl-containing quaternary ammonium salt-type long-chain siloxane, 30-38 parts of 1-methyl-3-phenyl-1H-pyrazole-5-carboxylic acid, and 6-15 parts of p-toluenesulfonic acid.

5. The method for preparing the dry-rot tree hole cleaning composition for ancient tree maintenance according to claim 1, characterized in that: In step S2, the reaction temperature is 100-130° C., and the reaction time is 12-24 hours.

6. The method for preparing the dry-rot tree hole cleaning composition for ancient tree maintenance according to claim 1, characterized in that: The components in step S3 are calculated by weight as follows: 100 parts of polyether polyol, 0.6-1.0 parts of triethylenediamine, 0.2-0.5 parts of stannous octoate, 9-15 parts of deionized water, 30-50 parts of toluene diisocyanate, and 2-15 parts of quaternary ammonium salt siloxane containing a pyrazole ring.

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