CN102814848B - Copper azole wood preservative and preparation method thereof - Google Patents
Copper azole wood preservative and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to a copper azole wood preservative and a preparation method thereof. The preservative comprises the following components in percentage by weight: 20-31% of copper, 40-61% of monoethanolamine, 5.2-19% of ammonia, 0.25-1.2% of triazole compound, 4-11% of organic solvent and 2.5-6% of surfactant and the balance of water. The preservative provided by the invention not only has favorable anticorrosion and vermin-proof properties for outdoor and indoor wood and bamboo, but also has the advantages of low corrosivity for metal, high stability, strong loss resistance, low consumption and low cost; and the method is simple and practical, does not need heating in the preparation process, and has the advantage of low production cost.
Description
Technical field
The present invention relates to class copper azole wood preservative and preparation method thereof, and the application in the preservative treatment of wood (bamboo) material.
Background technology
Wood preservation chemicals treatment can improve the endurance quality of timber.With traditional timber preservative CCA(chromated copper arenate) compared with, the more environmental protection of copper azole preservative, compared with ACQ preservative, copper azoles process dosage is lower, and cost is more cheap.Gareth Williams described in United States Patent (USP) RE36798 in 2000 consist of copper, Tebuconazole, amido alcohol preparation for wood preservative, in preparation, copper is combined with the form of complex compound with amido alcohol.Reimer Goettsche described copper, Cyproconazole, amido alcohol, surfactant/containing the preparation of phosphonium compounds for wood preservation in United States Patent (USP) 6441016B2 in 2002, wherein copper 2.5-45%, Cyproconazole 0.5-15%, amido alcohol 5-50%, surfactant 0.5-30%.But in this copper triazole preparation, the solvability of triazole in water is minimum, easily precipitates.
The timber used under outdoor conditions, after copper preservative process timber, its active ingredient fixation performance is in wood the key factor determining its antiseptic insect-repelling effect.INST OF WOOD INDUDTRY CHINESE reports that in ZL200310124153.9 the weight of copper triazole antiseptics for wood is composed as follows: copper 16-31%, triazole 0.7-6%, boride (calculating with boric acid) 0-26%, alcohols 4-6%, ammonia 0-47%, aminoethanol 6-60%, quaternary surfactant 1-4%, phosphate 0-1% are 0 when wherein ammonia is different with phosphatic content.Copper in preservative is bivalent cupric ion, comprising: copper sulphate, verdigris, copper chloride, copper oxide or Kocide SD.Adopt amino moiety in preparation or completely substitute monoethanolamine, or add a small amount of phosphate and can improve copper fixation rate in wood, increase the endurance quality of timber.Although copper fixation performance in wood and field endurance quality increase after this preservative process timber, but the large percentage of triazole and copper causes the usage amount of triazole higher, cost is high, adopt amino moiety or substitute this preservative of monoethanolamine completely and corrosion of metal is increased, add the deficiency that a small amount of phosphate exists preparation stability difference and produces precipitation in addition.
Summary of the invention
The object of this invention is to provide a kind of copper azole wood preservative and preparation method thereof, this preservative decapacitation has outside good antiseptic insect-repelling performance to outdoor and indoor wooden bamboo wood, also have corrosion of metal low, good stability, anti-current is lost strong, the advantage that usage amount is little and cost is low, and the method has simple and practical, without the need to adding hot preparation, the advantage that production cost is low.
For this reason, in copper azole wood preservative of the present invention, the weight percent composition of each component is: copper 20-31%, monoethanolamine 40-61%, ammonia 5.2-19%, triazole class compounds 0.25-1.2%, organic solvent 4-11%, surfactant 2.5-6%, all the other are for water.Described copper is cupric salt, is selected from verdigris, copper acetate.Described triazole class compounds is that at least one is selected from following compound: Cyproconazole, own azoles alcohol, epoxiconazole, Triadimenol; The ratio of described copper and Cyproconazole, own azoles alcohol, epoxiconazole, Triadimenol is between 80:1 and 60:1.Described triazole class compounds is propiconazole and Tebuconazole mixture.The ratio of described copper and propiconazole and Tebuconazole sum is between 30:1 and 20:1, and the proportion of propiconazole and Tebuconazole is between 1:0.8 to 1:1.2.Described organic solvent is the mixing of one or several in dimethylbenzene, toluene, glycerine, methyl alcohol.Described surfactant is a kind of in alkylaryl polyoxyethylene ether, aliphatic alcohol polyethenoxy base ether, alkylnaphthalene sulfonate, lignosulfonates, didecyldimethylammonium amine-oxides or several mixing.。
Prepare the method for copper azole wood preservative, comprising:
(1) first triazole solution is prepared: the triazole class compounds of aequum is dissolved at least one organic solvent, adds at least one surfactant, make it dissolve completely, make triazole solution;
(2), when preparing copper amine (ammonia) complex compound, first add water in reactor, add mantoquita fast, stir, more slowly add the ammoniacal liquor of monoethanolamine and 20%, limit edged stirs, control adds speed and prevents the ejection of reaction vigorous reaction liquid, after mantoquita dissolves completely, is cooled to 50-80 DEG C;
(3) add triazole solution in last copper amine (ammonia) complex compound, stir, make copper azole wood preservative.
At least containing the glycerine of 20-30% accounting for weight of solvent in described organic solvent.
Preparation of the present invention has following advantage:
(1) preservative reduces corrosion of metal performance.In preparation, copper is cupric salt, is selected from verdigris, copper acetate, and they are weak acid copper, greatly reduces corrosion of metal performance.
(2) add alkylaryl polyoxyethylene ether, aliphatic alcohol polyethenoxy base ether, amine-oxides etc. in preparation and be used as surfactant, compared with original surface activating agent, better improve the stability of preparation; In preparation, phosphate free is also without boron, and decrease preparation lability and produce the risk precipitated, preservative is placed and also produced without any precipitation for 3 years.
(3) the present invention is while guaranteeing antiseptic insect-repelling performance, considerably reduces the ratio of triazole and copper and the usage amount of triazole class compounds, reduces manufacturing cost, add the kind of triazole.
(4) in invention formulation the proportion of ammonia and monoethanolamine restriction and determine, ensure that preparation in use without the taste of ammonia, decrease preparation instability and produce precipitation and the risk higher to metal protection, also guarantee the leach resistance of its copper and triazole when outdoor application, fixation rate is in higher scope.
(5) when preparing preparation, the mixed solvent accounting for the glycerine of the 20-30% of weight of solvent compared with single solvent, at higher copper drugloading rate 3.19kg/m
3(triazole drugloading rate is respectively 0.0637 kg/m
3) time, the leach resistance (representing with fixation rate) of triazole can be improved.
In addition, preparation technology of the present invention, the order added and time, is made full use of the heat that anti-raw material should produce, is not needed other heating in whole production engineering by control reaction raw materials.
Compared with the like product that the present invention is known with prior art, composition of the present invention has the following advantages:
(1) composition of the present invention is lower to corrosion of metal;
(2), when preparing said composition, do not need heating, utilize the thermal release of reaction itself;
(3) because the present composition has the advantage that drug effect is high and usage amount is low, therefore processing cost is low, when in outdoor, (C3 service rating) uses the product after processing on the ground, the processing cost of medicament is suitable with CCA, only has the 25-30% of environmental friendly, anti-corrosive agent ACQ processing cost;
(4) stability of composition of the present invention is good, places 36 months still without layering or deposited phenomenon;
(5) leach resistance of the present composition is better, is specially adapted to the antisepsis and anti-insect treatment of outdoor and indoor wooden bamboo wood.
Said composition can be used for the process of the wooden bamboo wood of indoor and outdoor or Bamboo and wood product, described processing method adopts wooden bamboo wood or Bamboo and wood product vacuum pressed or normal pressure dipping method, and the wooden bamboo wood after process or Bamboo and wood product can be made to have the performance of good anticorrosion and insect protected.
Embodiment
Embodiment 1: preparation 1:
Copper 23.3%, propiconazole 0.48%, Tebuconazole 0.49%, normal propyl alcohol 5.0%, glycerine 2.6%, monoethanolamine 53.2%, ammonia 9.6%, polyoxyethylene nonylphenol ether 2.5% and didecyldimethylammonium amine-oxides 1.8%, all the other are water.
The preparation method of preparation 1:
2.0g 95% propiconazole and 2.0g 97% Tebuconazole are dissolved in 20g normal propyl alcohol and 10g glycerine, add 10g polyoxyethylene nonylphenol ether surfactant and 10g 70% didecyldimethylammonium amine-oxides, obtained solution A; 175g verdigris (copper content 54.5%), after adding 365g water, add 210g 99.5% monoethanolamine and add 25% ammoniacal liquor 150g, after verdigris dissolves completely, mix with above-mentioned obtained solution A, i.e. the preparation 1 (being called for short CuPT-A) of obtained 10.4% (in copper, propiconazole, Tebuconazole sum).
Embodiment 2: preparation 2:
Copper 24.7%, propiconazole 0.49%, Tebuconazole 0.50%, normal propyl alcohol 7.7%, monoethanolamine 54.2%, ammonia 9.7%, fatty alcohol-polyoxyethylene ether MOA-9 2.6%, all the other are water.
The preparation method of preparation 2:
2.0g 95% propiconazole and 2.0g 97% Tebuconazole are dissolved in 30g normal propyl alcohol, add 10g fatty alcohol-polyoxyethylene ether MOA-9, obtained solution A; 175g verdigris, after adding 375g water, add 210g monoethanolamine and add 25% ammoniacal liquor 150g, after verdigris dissolves completely, mix with above-mentioned obtained solution A, i.e. the preparation 2 (being called for short CuPT-B) of obtained 10.4% (in copper, propiconazole, Tebuconazole sum).
Embodiment 3: preparation 3:
Copper 27.0%, Cyproconazole 0.39%, normal propyl alcohol 6.5%, glycerine 1.7%, monoethanolamine 42.5%, ammonia 17.8%, fatty alcohol-polyoxyethylene ether MOA-9 2.0%, didecyldimethylammonium amine-oxides 2.0%, all the other are water.
The preparation method of preparation 3:
1.45g 95% Cyproconazole is dissolved in 24g normal propyl alcohol and 6g glycerine, adds 7g fatty alcohol-polyoxyethylene ether MOA-9 and 10g 70% didecyldimethylammonium amine-oxides, obtained solution B; 175g verdigris, after adding 330g water, add 150g monoethanolamine and add 25% ammoniacal liquor 250g, after verdigris dissolves completely, mix with above-mentioned obtained solution B, i.e. the preparation 3 (being called for short CuCy) of obtained 10.1% (in copper, Cyproconazole sum).
Performance test of the present invention illustrates:
1, the metal erosion performance of preparation 2
With reference to AWPA E17-99, clean metal test specimen, wiped clean, dries, and be suspended in after weighing in the glass jar that 400mL test medicament is housed, periodic cleaning is weighed, and tests immersion 30 days altogether.Medicament is gone out to corrosion of metal rate again according to AWPA E17-99 criterion calculation.The results are shown in Table 1.In table 1, preparation 2 pairs of Q235A steel corrosion rates are 0, and the rate of corrosion of low concentration preparation 2 pairs of red coppers is also lower than ACQ.Compared with the result of table 2 in document IRG/WP 06-40329, preparation 2 pairs of Q235A steel and red copper rate of corrosion than ACQ and each preparation of copper azoles all lower.
The rate of corrosion of table 1 preparation 2 pairs of Q235A steel and red copper
The leach resistance of the active ingredient 2, after preparation 1,2 and 3 process timber
Test method is with reference to the method for AWPA E11-2006, and the different preparation process timber inhaling dose, gas is dry carried out indoor water leaching test after 21 days, by sample grouping distilled water immersion 14 days, refreshed the water periodically and collected leachate.Measure the concentration of copper in leachate with Atomic Absorption Spectrometer, then calculate the fixation rate of medicament according to AWPA E11-97 standard.
In medicament, the leach resistance of copper the results are shown in Table 2.In table 2, for CuPT preparation, there is the fixation rate of the preparation copper of glycerine on the low side; When copper suction dose is suitable, after the examination material of preparation 1,2 and ACQ-B process, the fixation rate of copper is suitable.The fixation rate impact of same preparation copper when different drugloading rate is not obvious.
The leach resistance of copper in table 2 medicament
In medicament, the leach resistance of triazole the results are shown in Table 3.In table 3, for preparation 2, wherein do not add glycerine, at higher copper drugloading rate 2.14kg/m
3(triazole drugloading rate is respectively 0.043 kg/m
3) time, the fixation rate of triazole is 72.5-74.0%, comparatively has the preparation 1 of glycerine on the low side; The fixation rate of all the other drugloading rate Tebuconazoles, propiconazole is all close to or higher than 90%; For preparation 3, the fixation rate of Cyproconazole when two drugloading rate is all lower than 80%.
The leach resistance of triazole in table 3 medicament
3, the bacteriostasis property of triazole
Test method: with whiterot fungi (Trametes versicolor (L. ex Fr.) Pilat, be called for short TV) and brown rot fungus (Gloeophyllum trabeum (Pers. ex Fr.) Murr., be called for short GT) be wood decay bacterial classification, with reference to Pharmacopoeia of People's Republic of China--antibiotic microorganism determination method, potato dextrose agar (PDA) is medium, triazole 50% ethanol is prepared, and 50% ethanol is used in contrast.Contrast test bacterial classification non-activity, triazole is to TV inhibition zone result of the test table 4, and own azoles alcohol, epoxiconazole, Triadimenol are suitable with Cyproconazole to TV bacteriostatic activity.In table 4, all triazoles are all greater than 64 mm to GT inhibition zone pilot diameter in 0.01-0.1% concentration range, illustrate that they are all better to the inhibition of GT bacterium.
Table 4 pair TV inhibition zone result of the test (diameter, mm)
4, in Application Example 2,3, preparation 2 and 3 processes the laboratory antiseptic property of timber
Test method: with whiterot fungi (Trametes versicolor (L. ex Fr.) Pilat, be called for short TV) and brown rot fungus (Gloeophyllum trabeum (Pers. ex Fr.) Murr., be called for short GT) be wood decay bacterial classification, the method of professional standard LY/T1283-1998 " wood preservative is to rot fungi toxicity test room test method " is adopted to test, experimental result, in table 5, contrasts as the sample (lower same) not with preservative process.
The laboratory antiseptic property of table 5 chemicals treatment timber
5, the field endurance quality that preparation 2 and 3 processes timber is applied
The field long duration test that the field long duration test that preparation 2 processes examination material the results are shown in Table 6, CuCy process the results are shown in Table 7.
The data display of table 6, in field test site, Beijing, untreated control test specimen is after buried 2 years, and test specimen is all rotten, but without the erosion of termite moth.In field test place, Guangzhou untreated control after buried 2 years, test specimen all rotten or by termite moth erosion; The resistance to rotten and termite-proof moth erosion index of each process test specimen is 10.
Table 7 is visible, outdoor with contact service condition under (C4.1 uses and classifies), respectively process for CuCy, reasonable drugloading rate is positioned at 1.8-3.6 kg/m
3between.But in the very serious area of termite damage, CuCy drugloading rate >3.6 kg/m
3be recommended as the reasonable drugloading rate that C4.1 uses classification.
The intact value of table 6 preparation 2 field test sample
The intact value of table 7 CuCy field test sample
Claims (2)
1. a copper azole wood preservative, is characterized in that:
In this preservative, the weight percent of each component is: copper 20-31%, monoethanolamine 40-61%, ammonia 5.2-19%, triazole class compounds 0.25-1.2%, organic solvent 4-11%, surfactant 2.5-6%;
Described copper is cupric salt, is selected from verdigris, copper acetate, and described triazole class compounds is that at least one is selected from following compound: own azoles alcohol, epoxiconazole, Triadimenol,
The ratio of described copper and own azoles alcohol, epoxiconazole, Triadimenol is between 80:1 and 60:1, described organic solvent is the mixing of one or several in dimethylbenzene, toluene, glycerine, methyl alcohol, and described surfactant is the mixing of one or several in alkylaryl polyoxyethylene ether, aliphatic alcohol polyethenoxy base ether, alkylnaphthalene sulfonate, lignosulfonates.
2. prepare a method for the copper azole wood preservative described in claim 1, it is characterized in that: comprise,
(1) first triazole solution is prepared: the triazole class compounds of aequum is dissolved at least one organic solvent, adds at least one surfactant, make it dissolve completely, make triazole solution;
(2) when preparing copper complex, in reactor, first add water, add mantoquita fast, stir, more slowly add the ammoniacal liquor of monoethanolamine and 20%, limit edged stirs, control adds speed and prevents the ejection of reaction vigorous reaction liquid, after mantoquita dissolves completely, is cooled to 50-80 DEG C;
(3) add triazole solution in last copper complex, stir, make copper azole wood preservative.
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| CN103712876A (en) * | 2013-12-20 | 2014-04-09 | 南京工业大学 | Quick evaluation method of wooden building commonly-used structural wood natural corrosion resistance based on wood chemical component parameters |
| CN104085009B (en) * | 2014-06-11 | 2016-05-04 | 马鞍山市海滨水产品生态养殖专业合作社 | A kind of timber floor timber loses modification agent with easily oozing anti-current |
| CN104972533A (en) * | 2015-06-11 | 2015-10-14 | 李金新 | Copper triazole wood antiseptic agent and preparation method thereof |
| CN106003312B (en) * | 2016-08-04 | 2017-12-26 | 中国林业科学研究院木材工业研究所 | Triazole wood bamboo wood anti-corrosion Anti- tarnishing composition and preparation method thereof |
| JP2020502093A (en) * | 2016-12-16 | 2020-01-23 | コッパース パフォーマンス ケミカルズ インク． | Wood preservative and method for producing it |
| CN107283572A (en) * | 2017-08-25 | 2017-10-24 | 太仓优活生物技术有限公司 | A kind of organic solvent type timber preservative |
| CN108407003A (en) * | 2018-03-19 | 2018-08-17 | 浙江省林业科学研究院 | A kind of hot method for anticorrosion treatment of timber oil |
| CN114701029B (en) * | 2022-04-18 | 2023-06-02 | 中山市伍氏大观园家具有限公司 | Pretreatment process of rosewood |
| CN115416122A (en) * | 2022-08-25 | 2022-12-02 | 中国林业科学研究院木材工业研究所 | Preservative based on wood weak phase structure protection, preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5635217A (en) * | 1991-04-18 | 1997-06-03 | Dr. Wolman Gmbh | Wood preservatives |
| CN1633853A (en) * | 2003-12-31 | 2005-07-06 | 中国林业科学研究院木材工业研究所 | Novel copper and triazole antiseptics for wood |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5635217A (en) * | 1991-04-18 | 1997-06-03 | Dr. Wolman Gmbh | Wood preservatives |
| CN1633853A (en) * | 2003-12-31 | 2005-07-06 | 中国林业科学研究院木材工业研究所 | Novel copper and triazole antiseptics for wood |
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