CN1319456C - Novel copper and triazole antiseptics for wood - Google Patents

Abstract

The invention relates to a new class of copper triazole wood preservatives, the relative content of each component is: copper 16-31%, triazole 0.7-6%, boride (calculated by boric acid) 0-26%, alcohol 4- 6%, ammonia 0-47%, aminoethanol 6-60%, quaternary ammonium salt surfactant 1-4%, phosphate 0-1%, wherein the content of ammonia and phosphate is not 0 at the same time. Copper in the preparation can be combined with ammonia in the form of complexes, and its cost is lower than that of aminoethanol. When the preparation contains copper ammonium complex, its stability and copper fixation rate after wood treatment are equivalent to those of copper aminoethanol complex preparation. In addition to tebuconazole and cyproconazole, triazoles include propiconazole, and borides and a small amount of phosphate may be included in the preparation. The results of the field durability test show that the above preparations have better effects of corrosion resistance and termite resistance.

Description

Copper triazole wood preservative

Technical field The present invention relates to the composition of a new class of copper triazole wood preservatives, and its application in wood (bamboo) wood preservative treatment.

Background technology Wood is a biopolymer material, which is easily harmed and degraded by biological factors such as fungi and insects, such as decay and insects. Wood preservatives can overcome this defect. Compared with foreign developed countries, the application of anti-corrosion materials in China is relatively small, and its development potential is relatively large. In recent years, the domestic wood preservative industry has developed rapidly in the southern region, mainly dealing with a small amount of agricultural timber, garden timber and rubber wood furniture, some of which are exported. The preservatives currently used in China are mainly copper chromium arsenic (CCA), and a small amount of garden materials use copper quaternary ammonium (ACQ). CCA has been widely used at home and abroad, because after the wood treated with CCA exceeds its service life, it is difficult to treat waste wood, such as incineration and recovery of heavy metals, adsorption and recovery of heavy metals after microbial decomposition, etc. Chromium and arsenic in CCA are heavy metals, which have a great impact on the environment. They are strictly restricted in some countries, such as prohibiting their use in places where they are in contact with people. No CCA. Research on alternatives to CCA is urgent. In recent years, some copper (Cu)-based chromium-free, arsenic-free water-soluble preservatives such as: ACQ, copper azole (CuAz), Cu-HDO, bisdimethyldithioacid copper (CDDC), are being used worldwide widely used within.

In 2000, Gareth Williams introduced in US Patent RE36798 a preparation composed of copper, tebuconazole, and amino alcohol for use in wood preservatives. In the preparation, copper and amino alcohol are combined in the form of complexes. Reimer Goettsche introduced copper, cyproconazole, amino alcohol, surfactant/phosphonium-containing compound preparations for wood preservation in 2002 in U.S. Patent 6441016B2, wherein copper 2.5-45%, cyproconazole 0.5- 15%, amino alcohol 5-50%, surfactant 0.5-30%. In the copper triazole preparation, the solubility of the triazole in water is extremely small, and it is easy to precipitate, so an ionic surfactant should generally be added. Increasing the amount of amino alcohol in the preparation can partially overcome the instability of the preparation, but the cost of using the amino alcohol to form a complex with copper is relatively high.

After the wood is treated with copper preservatives, the fixation performance of its active ingredients in the wood is an important factor to determine its preservative effect, especially for wood used under outdoor conditions. There are many studies and reports on the fixation of CCA in wood, and the produced copper chromate is beneficial to the fixation in wood, while the fixation of some other copper preservatives is less reported. JiangM-L, et al reported in IRG/WP03-30316 that the results of indoor water loss experiments showed that the fixation rate of wood copper treated with organic acid copper salts such as copper citrate was not as good as ACQ.

SUMMARY OF THE INVENTION The biggest difference between the present invention and those reported in foreign invention patents is that copper in the preparation can be combined with ammonia in the form of a complex, and the cost of the preparation is lower than that of a preparation in which copper and amino alcohols are complexed; Triazoles include propiconazole in addition to tebuconazole and cyproconazole; the preparation may contain borides, a small amount of phosphate, or no borides and a small amount of phosphate; a small amount of quaternary ammonium salt cationic surface activity is added to the preparation agent and aminoethanol.

The composition by weight of the copper triazole wood preservative of the present invention is as follows: copper 16-31%, triazole 0.7-6%, boride (calculated as boric acid) 0-26%, alcohols 4-6%, ammonia 0-47% %, aminoethanol 6-60%, quaternary ammonium salt surfactant 1-4%, phosphate 0-1%, wherein the contents of ammonia and phosphate are not 0 at the same time.

The copper in the preservative of the present invention is divalent copper ion, including: copper sulfate, basic copper carbonate, copper chloride, copper oxide or copper hydroxide. When the triazole in the preparation is tebuconazole, the ratio of copper to tebuconazole is more suitable between 25:1 and 10:1, and the ratio of copper to ammonia is more suitable between 1:1.3 and 1:0.6. suitable.

When the triazole in the preparation is cyproconazole, the ratio of copper to cyproconazole is more suitable between 100:1 and 50:1, and the ratio of copper to ammonia is between 1:1.3 and 1:0.6 room is more appropriate.

When the triazole in the preparation is propiconazole (propiconazole), the ratio of copper to propiconazole is more suitable between 25:1 and 5:1, if the ratio is too low, propiconazole is easy to precipitate, and the amount of propiconazole The increase will increase the cost of the preparation; the preparation with too high ratio of copper to propiconazole has poor inhibitory effect on some putrefactive bacteria. When propiconazole is used, ammonia can be used as a ligand in the preparation, and a small amount of aminoethanol can be added. The amount of aminoethanol is not more than 1/8 of ammonia, and aminoethanol can also be used as a ligand. Ammonia is added.

When preparing the preparation, it is necessary to dissolve the triazole with organic solvents such as a small amount of alcohols, acetone, DMF, etc., and the alcohols include ethanol, propanol, and isopropanol. The results of the indoor water loss test show that the fixation rate of copper in the preparation using ammonia water as a ligand in the present invention is higher than or equivalent to the preparation using aminoethanol as a ligand.

Adding a quaternary ammonium salt cationic surfactant in the preparation can improve the stability of the preparation, and the triazole will not precipitate. The ratio of the amount of copper to the quaternary ammonium salt cationic surfactant is preferably between 16:1 and 6:1. In addition, the quaternary ammonium salt cationic surfactant itself also has certain antifungal activity, and the price is relatively suitable. Quaternary ammonium salt surfactants include didecyl dimethyl ammonium chloride (DDAC), dodecyl benzyl dimethyl ammonium chloride (BAC), double octadecyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, Dialkyl dimethyl ammonium chloride, octadecyl dedecyl dimethyl ammonium chloride, coco trimethyl ammonium chloride or the anion in the above quaternary ammonium salt compounds is bromine.

The preparation may contain borides, such as boric acid or sodium tetraborate (borax), or may be boride-free. The addition of the boride does not reduce the stability of the preparation and does not lead to the precipitation of copper or triazole active ingredients. When there are borides, the ratio of copper to borides (in boric acid) is more suitable between 2: 1 and 1: 2. When the wood used under the outdoor and ground contact conditions is used for antiseptic treatment with the preparation of the present invention, it can reduce The amount of boride used or no boride used. When the wood used indoors without contact with the ground is treated with the preparation of the present invention, borides may not be added to the preparation.

When the preparation is stored for more than 6 months, the stability of the preparation can be improved by adding a small amount of aminoethanol while the ammonia is complexed with most of the copper, and the copper will not precipitate.

Phosphate can significantly improve the fixation rate of copper in some copper preparations, but the amount of phosphate should not be large, and the ratio of phosphate to copper is below 10:1. The larger the amount of phosphate added, the worse the stability of the preparation. Phosphates include diammonium hydrogen phosphate, ammonium dihydrogen phosphate.

Formulations 1-7 and Examples 1-4 can illustrate the present invention in more detail, but the content of the present invention is not limited to Formulations 1-7 and Examples 1-4.

DETAILED DESCRIPTION Preparation 1 copper 16%, boric acid 16%, propiconazole 0.7%, ethanol 5%, aminoethanol 60%, didecyl dimethyl ammonium chloride surfactant 1%, phosphate 1%.

Preparation 2

Copper 16%, boric acid 16%, tebuconazole 0.7%, ethanol 5%, aminoethanol 60%, didecyl dimethyl ammonium chloride surfactant 1%, phosphate 1%.

Preparation 3

Copper 25%, boric acid 25%, tebuconazole 1%, ammonia water 31%, ethanol 6%, aminoethanol 8%, didecyldimethylammonium chloride surfactant 4%.

Preparation 4

Copper 25%, boric acid 25%, propiconazole 1%, ammonia water 31%, ethanol 6%, aminoethanol 8%, didecyl dimethyl ammonium chloride surfactant 4%.

Preparation 5

Copper 37%, Tebuconazole 1.5%, Ammonia 47%, Ethanol 6%, Aminoethanol 6%, Didecyldimethylammonium chloride surfactant 2.5%.

Preparation 6

Copper 37%, propiconazole 13%, ammonia water 47%, ethanol 6%, aminoethanol 6%, dodecyl benzyl dimethyl ammonium chloride 2.5%.

Preparation 7

Copper 37%, cyproconazole 0.6%, ammonia water 47%, ethanol 6%, aminoethanol 6%, dodecyl benzyl dimethyl ammonium chloride 2.5%.

The preparation of example 1 preparation 4

1.2g propiconazole was dissolved in 10g ethanol, added 10g aminoethanol and 6.9g of 70% didecyl dimethyl ammonium chloride surfactant, made solution A: 115.5g copper sulfate (containing 5 crystal water ), after adding 357g of water for dissolving, add 25% ammonia 147g, then add 5.5% boric acid 528g for dissolving, and mix with the above-mentioned prepared solution A to obtain 5.1% (in terms of the sum of copper, propiconazole and boric acid) Preparation 4.

The preparation method of other preparations is with example 1.

Example 2 The anti-loss performance of some formulations after treating wood

According to the method of AWPA E11-97, the wood was treated with preparations of different drug absorption amounts, and after 21 days of air drying, the indoor water loss test was carried out. The samples were divided into groups and soaked in distilled water for 14 days, and the water was changed regularly and the leachate was collected. The concentration of copper in the leachate was measured with an atomic absorption spectrometer, and then the fixation rate of the agent was calculated according to the AWPA E11-97 standard. The results are shown in Table 1.

In Table 1, ammonia water or aminoethanol has little effect on the fixation rate of copper in the preparation; when the amount of copper absorption is equivalent, the fixation rate of copper after preparation 2, 3, 5 and the test material treated with ACQ-B is equivalent. The fixation rate of copper is generally higher than that of low drug absorption when the preparation has high drug absorption.

Table 1 Copper fixation rate of some preparations in slash pine preparation Drug absorption ^* (kg/m ³ ) Fixation rate (%) 2 2.197.15 85.486.0 3 2.187.30 83.488.4 5 1.143.69 85.489.2 ACQ-B 2.356.56 83.789.4

^* Note: The absorption amount of preparations 2, 3, and 5 is calculated by the sum of copper, triazole, and boric acid,

ACQ-B drug absorption is calculated as the sum of CuO and DDAC.

Indoor corrosion resistance after some preparations of example 3 handle bamboo

Corrosion resistance test method: adopt GB/T 13942.1-92 method, strains: Corious versicolor (C.v), Poria placenta (P.p); test material is moso bamboo, size: 20mm(L)×20mm(T)×5mm(R) .

Preparations 1-4 have a certain inhibitory effect on the white rot fungus Corious versicolor and the brown rot fungus Poria placenta when the drug absorption is 1.8-7.6kg/m ³ . The natural rot resistance of the moso bamboo used in this test is slightly rot resistant, and the weight loss of the control test material is between 10-20%.

Table 2 Indoor corrosion resistance test results of bamboo treated with some formulations preparation Drug absorption (Kg/M ³ ) Weight loss %Cv Drug absorption (Kg/M ³ ) Weight loss %Pp control 0 12.8 0 11.9 1 2.14.77.3 0.30.30.7 1.84.66.6 2.01.01.6 2 2.24.67.2 1.91.01.2 1.94.56.9 2.01.81.4 3 2.14.97.6 0.90.71.0 1.84.27.1 1.51.41.3 4 2.14.96.9 1.20.50.2 2.24.47.2 1.71.21.4

Example 4 The field durability after some formulations are treated with wood

Field durability test method: adopt ASTM D 1758-96, Populus tomentosa test material size: 20mm×20mm×300mm(L), Moso bamboo test material size: 30mm(T)×5-7mm(R)×300mm(L), reserve The thickness (R) of the moso bamboo test material was not processed, the test location: Shahe, Guangzhou, Guangdong, and the test period: December.

Preparations 1-7 have different antiseptic effects on Populus tomentosa, while the control samples are completely decayed or termite-eating (Table 3). In Table 4, some preparations have better antiseptic effects on moso bamboo. After the test period of 18 months, the rot and termite durability ratings of the control moso bamboo are both 0.

Table 3 The field durability of Populus tomentosa treated with the formulation (December) preparation Drug absorption (Kg/M ³ ) Durability Classification decay termite control 0 0 0 1 2.706.3411.4 8.29.69.6 101010 2 1.914.035.19 7.288.8 8.48.69.6 3 1.694.276.80 6.699.2 5.299 4 1.474.406.17 7.67.89.2 6.48.68.6 5 1.902.98 9.210 9.210 6.1210.5 9.610 1010 6 2.295.2911.1 9.89.410 101010 7 2.00 9.8 10

Table 4 The field durability (December) of the preparations after treatment of Moso bamboo preparation Drug absorption (Kg/M ³ ) Durability Classification decay termite control 0 5.2 2 2 1.324.345.42 98.89.6 101010 5 1.843.30 1010 1010 6 2.353.40 1010 1010

Claims (14)

1. copper triazole wood preservative, the weight composition of this preservative is as follows: copper 16-31%, triazole 0.7-6%, boride (calculated in boric acid) 0-26%, alcohols 4-6%, ammonia 0-47%, aminoethanol 6-60%, quaternary ammonium salt cationic surfactant with antifungal activity 1-4%, and phosphate 0-1%, provided that the content of ammonia and phosphate is not zero at the same time. 2. The wood preservative according to claim 1, wherein said copper is a divalent copper ion compound selected from copper sulfate, basic copper carbonate, copper chloride, copper oxide or copper hydroxide. 3. The wood preservative according to claim 1, wherein said triazole is propiconazole. 4. A wood preservative according to claim 3, wherein the ratio of copper to propiconazole is between 25:1 and 5:1. 5. The wood preservative according to claim 1, wherein said triazole is tebuconazole. 6. A wood preservative according to claim 5, wherein the ratio of copper to tebuconazole is between 25:1 and 10:1 and the ratio of copper to ammonia is between 1:1.3 and 1:0.6. 7. The wood preservative according to claim 1, wherein said triazole is cyproconazole. 8. A wood preservative according to claim 7, wherein the ratio of copper to cyproconazole is between 100:1 and 50:1 and the ratio of copper to ammonia is between 1:1.3 and 1:0.6. 9. The wood preservative according to claim 1, wherein said boride is sodium tetraborate, boric acid or mixtures thereof. 10. A wood preservative according to claim 9, wherein when said wood preservative contains borides, the ratio of copper to boride, calculated as boric acid, is between 2:1 and 1:2. 11. The wood preservative according to claim 1, wherein said alcohol is ethanol, propanol or isopropanol. 12. according to the wood preservative of claim 1, wherein said quaternary ammonium salt cationic surfactant is didecyl dimethyl ammonium chloride (DDAC), dodecyl benzyl dimethyl ammonium chloride ( BAC), bis-octadecyldimethylammonium chloride, didodecanyldimethylammonium chloride, octadecyldecyldimethylammonium chloride, or cocotrimonium chloride, or It is the above-mentioned quaternary ammonium salt compound whose anion is a bromide ion. 13. The wood preservative according to claim 1, wherein said phosphate is diammonium phosphate or ammonium dihydrogen phosphate. 14. The application of the copper triazole wood preservative of any one of claims 1-13 in wood, bamboo or wooden material preservative treatment.