CN112476682A - Microemulsion type wood and bamboo preservative and preparation method thereof - Google Patents
Microemulsion type wood and bamboo preservative and preparation method thereof Download PDFInfo
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- CN112476682A CN112476682A CN202011392792.3A CN202011392792A CN112476682A CN 112476682 A CN112476682 A CN 112476682A CN 202011392792 A CN202011392792 A CN 202011392792A CN 112476682 A CN112476682 A CN 112476682A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/08—Impregnating by pressure, e.g. vacuum impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/343—Heterocyclic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/36—Aliphatic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/50—Mixtures of different organic impregnating agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K2240/00—Purpose of the treatment
- B27K2240/20—Removing fungi, molds or insects
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The invention relates to a microemulsion type wood and bamboo preservative and a preparation method thereof. The microemulsion type wood and bamboo preservative comprises the following components in percentage by weight: 0.002-0.32% of original methoxy acrylate, 0.001-0.1% of insecticidal component, 0.009-1.1% of organic solvent, 0.001-0.012% of cosolvent, 0.001-0.9% of antifreeze, 0.007-1.2% of surfactant, 0-0.6% of penetrating agent, 0-0.3% of defoaming agent and the balance of water. The microemulsion type wood and bamboo preservative for secondary treatment is prepared by adding 0.1-0.9 percent of polyacrylic acid and 0.1-0.9 percent of nano titanium dioxide in percentage by weight into residual liquid after wood and bamboo are treated by the microemulsion type wood and bamboo preservative for primary treatment. The wood treated by the preservative has higher preservative performance, and also has the advantages of small dosage of medicament, good preparation stability, strong leaching resistance, good hydrophobic light resistance, simple method operation and low cost.
Description
Technical Field
The invention belongs to the field of wood preservation, and particularly relates to a microemulsion type wood and bamboo preservative as well as a preparation method and application thereof.
Background
Wood has become an important material in economic construction of countries in the world as a material with light weight, large strength-to-weight ratio and sustainable utilization. Wood is a plant material with obvious biological characteristics, and is extremely vulnerable to microorganisms during growth or processing and use. Therefore, certain measures need to be taken to protect the wood and bamboo from being degraded by decay fungi, and the preservative treatment is the best way for prolonging the service life of the wood and bamboo and protecting forest resources.
At present, the preservative is mainly Copper Chromite Arsenate (CCA) in China, and chromium and arsenic are harmful heavy metals and can cause harm to human bodies. The ammonia soluble Alkylamine Copper (ACQ) treated wood has better corrosion prevention and termite prevention performance and excellent anti-loss performance, but the high use cost is an important problem. The copper azole preservative is an environment-friendly high-efficiency preservative, is produced and applied by various domestic enterprises, but has a darker color as copper preservatives like CCA and ACQ, and treated wood cannot keep the natural color of the wood and has a corrosion effect on metal connecting pieces of wood structures, so that the application range of the preservative is limited to a certain extent.
The Strobilurin fungicide is derived from a natural antibiotic Strobilurin A with bactericidal activity. Since the discovery of bactericidal activity, the successful development of the bactericide is finally realized through over twenty years of structural optimization and biological activity verification, and a new milestone is established after triazole bactericides in the development history of the bactericide. The bactericide is a novel agricultural bactericide with unique action mechanism, great development potential and market activity. The azoxystrobin, the kresoxim-methyl and the pyraclostrobin are typical representatives of strobilurin bactericides and have good activity on almost all fungal steel (ascomycetes, basidiomycetes, oomycetes and fungi imperfecti) diseases. The strobilurin fungicide has a strong inhibition effect on ascomycetes and basidiomycetes of wood decay, has good biocompatibility, and meets the requirements of high efficiency and environmental protection.
The raw medicine is insoluble in water, can be used for wood preservation treatment only by being prepared into a specific preparation, and simultaneously requires that the effective components of the preparation have higher anti-losing performance. Chinese patents CN106003312B and CN101530077B disclose kresoxim-methyl and azoxystrobin preparations, but the kresoxim-methyl and azoxystrobin preparations are only applied to control of agricultural diseases, do not relate to the content of wood preservation, and do not contain insecticidal components. Although the Chinese patents CN102232387A and CN106003312A disclose the anticorrosive composition containing triazole, the fixation rate of tebuconazole, cyproconazole, triadimenol and the like is only 50 percent to 70 percent, the loss is serious, and the outdoor use of the composition is limited.
The prior preservative has the advantages that various medicaments with the effects of sterilization, corrosion prevention and the like are generally used in large amount, so that the use cost is high, and the requirements of high efficiency and environmental protection are not met. The invention relates to a methoxy acrylic ester microemulsion type wood preservative which is high in efficiency, low in dosage of a medicament and strong in anti-losing ability.
Disclosure of Invention
The invention aims to provide a micro-emulsion type wood preservative and a preparation method thereof, wherein wood treated by the preservative has higher preservative performance, and the preservative has the advantages of small dosage of a medicament, good preparation stability, strong leaching resistance, good hydrophobic light resistance, simple method operation and low cost.
Therefore, the microemulsion type wood and bamboo preservative comprises a microemulsion type wood and bamboo preservative for primary treatment of wood and bamboo and a microemulsion type wood and bamboo preservative for secondary treatment of the primarily treated wood and bamboo.
The microemulsion type wood and bamboo preservative for primary treatment comprises the following components in percentage by weight: 0.002-0.32% of original methoxy acrylate, 0.001-0.1% of insecticidal component, 0.009-1.1% of organic solvent, 0.001-0.012% of cosolvent, 0.001-0.9% of antifreeze, 0.007-1.2% of surfactant, 0-0.6% of penetrating agent, 0-0.3% of defoaming agent and the balance of water. The microemulsion type wood and bamboo preservative for secondary treatment is prepared by adding 0.1-0.9 percent of polyacrylic acid and 0.1-0.9 percent of nano titanium dioxide in percentage by weight into residual liquid after wood and bamboo are treated by the microemulsion type wood and bamboo preservative for primary treatment.
Preferably, the microemulsion-type wood and bamboo preservative for one-time treatment comprises the following components in percentage by weight: 0.008-0.2% of methoxyl acrylate original drug, 0.009-0.010% of insecticidal component, 0.010-1% of organic solvent, 0.009-0.01% of cosolvent, 0.009-0.7% of antifreeze agent, 0.010-1% of surfactant, 0-0.6% of penetrating agent, 0-0.3% of defoaming agent and the balance of water; the microemulsion type wood and bamboo preservative for secondary treatment is prepared by adding 0.1-0.5 percent of polyacrylic acid and 0.1-0.5 percent of nano titanium dioxide in percentage by weight into residual liquid after wood and bamboo are treated by the microemulsion type wood and bamboo preservative for primary treatment.
Preferably, the input rate of the wood and bamboo preservative on the wood edge wood is more than or equal to 85 percent, the penetration depth on the surface of the bamboo chip is more than or equal to 2mm, the penetration depth on the surface of the bamboo integrated material is more than or equal to 1mm, and the wood and bamboo preservative is applied to the control of wood rot fungi, bamboo color changing fungi and mould and the protection of ancient building wood members.
Preferably, the strobilurin technical is one or more of azoxystrobin, kresoxim-methyl and pyraclostrobin;
preferably, the polyacrylic acid can be replaced by one of polyurethane, emulsified paraffin, plant tung oil and wood wax oil or any combination thereof.
Preferably, the insecticidal component is one or more of imidacloprid, thiamethoxam, permethrin, lambda-cyhalothrin and fipronil.
Preferably, the organic solvent comprises one or more of petroleum ether, cyclohexane, dichloromethane, diethyl ether, tetrahydrofuran, cyclohexanone, acetone, methyl butanone, acetonitrile, N-methyl-formanilide, N-methyl pyrrolidone, methyl acetate, ethyl acetate, dimethyl sulfoxide, methanol, ethanol, propanol, isopropanol, polyvinyl alcohol and the like in any combination.
Preferably, the cosolvent is selected from one or more of potassium iodide, benzoic acid, sodium benzoate, ethylenediamine and polyvinylpyrrolidone.
Preferably, the antifreeze agent is selected from one or more of ethylene glycol, propylene glycol, glycerol, urea, polyethylene glycol and sorbitol.
Preferably, the surfactant is selected from one or more of the following compounds: sodium dodecyl sulfate, calcium dodecyl benzene sulfonate, polysorbate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, benzyl phenol polyoxyethylene polyoxypropylene ether, dodecyl dimethyl amine oxide, hexadecyl dimethyl ammonium oxide, didecyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, and coco trimethyl ammonium chloride;
preferably, the defoaming agent is selected from one or more of silicone oil, natural oil and fat, polyether and C12-C22 higher alcohols;
preferably, the penetrant is selected from one or more of sodium di-sec-octyl sulfosuccinate, kerosene and azone.
A method for preparing a microemulsion type wood and bamboo preservative comprises the following steps:
(1) the preservative for primary treatment comprises the following components in percentage by weight: 0.002-0.32% of methoxyl acrylate original drug, 0.001-0.1% of insecticidal component, 0.009-1.1% of organic solvent, 0.001-0.012% of cosolvent, 0.001-0.9% of antifreeze agent, 0.007-1.2% of surfactant, 0-0.6% of penetrating agent, 0-0.3% of defoaming agent and the balance of water;
(2) dissolving the original medicine in an organic solvent, adding a cosolvent, stirring and dissolving, adding a surfactant, an anti-freezing agent, a defoaming agent and a penetrating agent after the original medicine is completely dissolved, stirring uniformly, and adding water which is 10 times of the weight of the original medicine to prepare a primary treatment preservative;
(3) adding water which accounts for 100-1000 times of the weight of the primary treatment preservative, diluting to obtain a primary microemulsion type wood preservative, placing the primary microemulsion type wood preservative in a closed treatment tank, and carrying out vacuum pressurization treatment on a wood material in the tank, wherein the primary microemulsion type wood preservative in the tank is supposed to submerge the upper end surface of the wood material;
the wood material is radiata pine, masson pine, pinus sylvestris, douglas fir, southern pine, red pine, poplar, fir, rubber wood, bamboo wood and laminated wood thereof;
(4) vacuumizing the closed treatment tank for 10-30 min under the initial vacuum of-0.09 MPa, then pressurizing for 1-1.5 MPa for 60-120 min under the later vacuum of-0.09 MPa for 15-20 min, releasing the pressure, and collecting the residual liquid in the closed treatment tank;
(5) taking out the wood material in the closed treatment tank, and drying the wood material in a drying kiln until the water content is 12-20% to obtain a primary treatment anticorrosive wood material;
(6) adding 0.1-0.9 wt% of polyacrylic acid and 0.1-0.9 wt% of nano titanium dioxide into the collected residual liquid of the closed treatment tank, and uniformly stirring to obtain a secondary microemulsion wood preservative; the particle size of the nano titanium dioxide is 20-30 nm;
the polyacrylic acid can be replaced by one or any combination of polyurethane, emulsified paraffin, plant tung oil and wood wax oil;
(7) and (3) carrying out secondary treatment on the obtained primary-treatment anticorrosive wood material by using a secondary microemulsion type wood preservative, wherein the secondary treatment comprises the following steps:
(a) spraying the secondary microemulsion type wood preservative on the surface of the wood of the primary treatment anticorrosive wood material, uniformly spraying, naturally drying a spraying layer, then spraying the next layer, repeating for 5-8 times to obtain the treatment anticorrosive wood material;
(b) and soaking the primary-treatment anticorrosive wood material in a secondary microemulsion type wood preservative for 3-4 days, taking out the soaked wood material, and drying the soaked wood material in a drying kiln until the water content is 12-20% to obtain the treated anticorrosive wood material.
The wood treated by the preservative has higher preservative performance, and also has the advantages of small dosage of the medicament, good stability of the preparation, strong leaching resistance, good hydrophobic light resistance, simple method operation and low cost.
The invention treats the wood and bamboo, has better control performance on white rot fungi and brown rot fungi, and can reach the antiseptic effect. Has obvious effect of preventing and controlling bamboo chameleon and mould.
The wood preservative can be used for protecting ancient building wood members, and is convenient to apply to ancient building protection.
Compared with the similar products known in the prior art, the wood preservative has the following advantages: (1) the preservative is water-borne, can form a stable microemulsion system after being diluted by water, belongs to a thermodynamically stable system, is not easy to break emulsion, has good microemulsion permeability, and can permeate into wood. (2) The preservative has good stability, does not have demulsification phenomenon after being placed for 6 months, and does not have crystal precipitation after being placed for 6 months after being diluted by water. (3) The preservative has strong anti-loss performance, can reduce the loss of the medicament when used outdoors, prolongs the protection time and reduces the influence on the environment. (4) The invention adopts the micro-emulsion type wood and bamboo preservative for primary treatment, the micro-emulsion type wood and bamboo preservative for secondary treatment of the wood and bamboo subjected to primary treatment and the treatment method, so that the wood and bamboo treated by the invention has good corrosion resistance and antibacterial performance, and also has the functions of hydrophobicity, oleophobicity, photocatalysis, light aging resistance and repairability. (5) The invention has high drug effect and low usage amount, thus having low usage cost and good environmental protection effect, and is a water-soluble colorless preservative which does not affect the color and the pattern of the wood after treatment.
Detailed Description
The invention is further illustrated by the following examples. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation. The methods in the following examples are conventional methods unless otherwise specified. The materials are commercially available from the open literature unless otherwise specified.
Example 1:
weighing 21g of 97% azoxystrobin, putting the azoxystrobin in a 1000ml three-neck flask, adding 140g of tetrahydrofuran and 2g of benzoic acid cosolvent, stirring to dissolve prothioconazole, respectively adding 80g of 80% didecyl dimethyl ammonium chloride, 20g of 70% dodecyl trimethyl ammonium chloride, 10g of ethylene glycol, 1g of silicone oil and 2g of azone, and stirring for 5 minutes by using a stirrer at the rotation speed of 200-1200 r/min. And adding 24g of water after uniformly stirring to obtain an azoxystrobin preparation, and adding water which accounts for 100-1000 times of the weight of the original medicine to dilute to obtain the primary microemulsion type wood preservative. And (3) placing the primary microemulsion type wood preservative in a closed treatment tank, and carrying out vacuum pressurization treatment on the wood material in the tank, wherein the primary microemulsion type wood preservative in the tank should submerge the upper end surface of the wood material. Vacuumizing the closed treatment tank for 10-30 min under the initial vacuum of-0.09 MPa, then pressurizing for 1-1.5 MPa for 60-120 min under the later vacuum of-0.09 MPa for 15-20 min, releasing the pressure, and collecting the residual liquid in the closed treatment tank. And taking out the wood material in the closed treatment tank, and drying the wood material in a drying kiln until the water content is 12-20% to obtain the primary treatment anticorrosive wood material. And adding 0.1-0.9 wt% of polyacrylic acid and 0.1-0.9 wt% of nano titanium dioxide into the collected residual liquid of the closed treatment tank, and uniformly stirring to obtain the secondary microemulsion wood preservative. And spraying the secondary microemulsion type wood preservative on the surface of the wood of the primary treatment anticorrosive wood material, uniformly spraying, naturally drying the sprayed layer, spraying the next layer, and repeating for 5-8 times to obtain the treated anticorrosive wood material.
Example 2:
weighing 21g of 98% kresoxim-methyl in a 1000ml three-neck flask, adding 120g of dimethylformamide and 2g of benzoic acid cosolvent, stirring to dissolve the kresoxim-methyl, respectively adding 110g of calcium dodecyl benzene sulfonate, 14g of glycerol, 1g of silicone oil and 2g of sodium di-sec-octyl sulfosuccinate, and stirring for 5 minutes by using a stirrer at the rotation speed of 200-1200 r/min. And (3) adding 30g of water after uniformly stirring to obtain a kresoxim-methyl preparation, and adding water accounting for 500 times of the weight of the original medicine to dilute to obtain the primary microemulsion type wood preservative. And (3) placing the primary microemulsion type wood preservative in a closed treatment tank, and carrying out vacuum pressurization treatment on the wood material in the tank, wherein the primary microemulsion type wood preservative in the tank should submerge the upper end surface of the wood material. Vacuumizing the closed treatment tank for 10-30 min under the initial vacuum of-0.09 MPa, then pressurizing for 1-1.5 MPa for 60-120 min under the later vacuum of-0.09 MPa for 15-20 min, releasing the pressure, and collecting the residual liquid in the closed treatment tank. And taking out the wood material in the closed treatment tank, and drying the wood material in a drying kiln until the water content is 12-20% to obtain the primary treatment anticorrosive wood material. And adding 0.5 weight percent of polyurethane and 0.8 weight percent of nano titanium dioxide into the collected residual liquid of the closed treatment tank, and uniformly stirring to obtain the secondary microemulsion type wood preservative. And soaking the primary treated anticorrosive wood material in a secondary microemulsion type wood preservative for 3-4 days, taking out the soaked wood material, and drying in a drying kiln until the water content is 15% to obtain the treated anticorrosive wood material.
Example 3:
weighing 21g of 98% pyraclostrobin, putting the pyraclostrobin into a 1000ml three-neck flask, adding 100g of ethanol and 2g of benzoic acid cosolvent, stirring to dissolve the pyraclostrobin, respectively adding 120g of tristyrylphenol polyoxypropylene polyoxyethylene ether, 14g of glycerol, 1g of silicone oil and 2g of di-sec-octyl sulfosuccinate sodium salt, and stirring for 5 minutes by using a stirrer at the rotating speed of 200-1200 r/min. And (3) adding 40g of water after uniformly stirring to obtain a pyraclostrobin preparation, and adding water accounting for 900 times of the weight of the raw pesticide for diluting to obtain the primary microemulsion type wood preservative. And (3) placing the primary microemulsion type wood preservative in a closed treatment tank, and carrying out vacuum pressurization treatment on the wood material in the tank, wherein the primary microemulsion type wood preservative in the tank should submerge the upper end surface of the wood material. And vacuumizing the closed treatment tank for 10-30 min under the initial vacuum of-0.09 MPa, then pressurizing for 1-1.5 MPa for 110min under the later vacuum of-0.09 MPa for 15-20 min, releasing the pressure, and collecting the residual liquid in the closed treatment tank. And taking out the wood material in the closed treatment tank, and drying the wood material in a drying kiln until the water content is 15% to obtain the primary treatment anticorrosive wood material. And adding 0.6 weight percent of emulsified paraffin and 0.9 weight percent of nano titanium dioxide into the collected residual liquid of the closed treatment tank, and uniformly stirring to obtain the secondary microemulsion type wood preservative. And spraying the secondary microemulsion type wood preservative on the surface of the wood of the primary treatment anticorrosive wood material, uniformly spraying, naturally drying the sprayed layer, spraying the next layer, and repeating for 5-8 times to obtain the treated anticorrosive wood material.
Example 4:
weighing 11g of 97% azoxystrobin and 11g of 98% pyraclostrobin into a 1000ml three-neck flask, adding 100g of cyclohexanone, 20g of isopropanol and 2g of benzoic acid cosolvent, stirring to dissolve the pyraclostrobin, respectively adding 90g of 80% didecyl dimethyl ammonium chloride, 20g of 70% octadecyl trimethyl ammonium chloride, 14g of propylene glycol, 1g of silicone oil and 2g of sodium di-sec-octyl sulfosuccinate, and stirring for 5 minutes by using a stirrer at the rotating speed of 200-1200 r/min. And (3) adding 30g of water after uniformly stirring to obtain a pyraclostrobin preparation, and adding water accounting for 800 times of the weight of the raw pesticide for diluting to obtain the primary microemulsion type wood preservative. And (3) placing the primary microemulsion type wood preservative in a closed treatment tank, and carrying out vacuum pressurization treatment on the wood material in the tank, wherein the primary microemulsion type wood preservative in the tank should submerge the upper end surface of the wood material. Vacuumizing the closed treatment tank for 10-30 min under the initial vacuum of-0.09 MPa, then pressurizing for 1-1.5 MPa for 60-120 min under the later vacuum of-0.09 MPa for 15-20 min, releasing the pressure, and collecting the residual liquid in the closed treatment tank. And taking out the wood material in the closed treatment tank, and drying the wood material in a drying kiln until the water content is 12-20% to obtain the primary treatment anticorrosive wood material. And adding 0.5 percent by weight of plant tung oil and 0.8 percent by weight of nano titanium dioxide into the collected residual liquid of the closed treatment tank, and uniformly stirring to obtain the secondary microemulsion type wood preservative. And soaking the primary treated anticorrosive wood material in a secondary microemulsion type wood preservative for 3-4 days, taking out the soaked wood material, and drying in a drying kiln until the water content is 15% to obtain the treated anticorrosive wood material.
Test data: the dilution stability and the freezing resistance of the formulations of examples 1-4 are as follows:
the preparations of examples 1 to 4 (the primary treatment preservative before preparation of the primary microemulsion type wood preservative) were diluted 500 times with water, and the water dilution performance was observed, and the diluted drug solution was continuously observed for 6 months to evaluate the stability with time, and the results are shown in table 1.
Table 1 water solubility and stability data for formulations
As can be seen from Table 1, the preparations of examples 1 to 4 had good water solubility, and were all clear and transparent solutions after dilution with water, and no crystal precipitated after the diluted medicinal solution was left for 6 months. The data show that the prepared preparation has good water solubility and high stability, and can meet the requirements of antiseptic treatment on the preparation.
The frost resistance of the preparations (primary microemulsion type wood preservative and secondary treatment microemulsion type wood and bamboo preservative) in the embodiments 1 to 4 is shown in table 2, and the frost resistance of all the preparations is excellent at-10 ℃ for 240 hours.
TABLE 2 Freeze resistance at-10 ℃ of the partial formulations
Examples 1-4 indoor corrosion resistance of formulations (primary microemulsion type wood preservative and secondary treatment microemulsion type wood and bamboo preservative) treated wood:
the brown rot fungi adopt Gloeophyllum trabeum (Gt), the white rot fungi adopt Coriolus versicolor (Tv) to carry out indoor wood corrosion resistance experiments, and the experiments are carried out according to forestry industry standard LYT 1283 and 2011 laboratory experiment method for toxicity of wood preservatives to rot fungi. The results are shown in Table 3, and the control is a sample of untreated material.
As can be seen from Table 3, the formulations prepared in this example all had a high preservative performance when used to treat radiata pine. Wherein the drug loading rate of azoxystrobin, kresoxim-methyl and pyraclostrobin is 0.31-0.46 kg/m3When the strain is used, the mass loss rate (WL) of the strain to the white rot fungi is less than 5 percent, and the effect to the brown rot fungi is more obviousRemarkably, at low drug loading rates of 0.22kg/m3When the composition is used, the inhibition rates of the three preparations are less than 5 percent; the composite preparation 4 of azoxystrobin and pyraclostrobin has more excellent effect compared with a single preparation, and the mass loss rate of the composite preparation to two bacteria is less than 5% under three drug-loading levels.
TABLE 3 indoor Corrosion resistance test results of Pinus radiata preparations
Example 1-4 preparation (primary microemulsion type wood preservative and secondary treatment microemulsion type wood and bamboo preservative) bamboo wood treatment anti-discoloration performance:
test materials: moso bamboo chips with the test piece size of 50 multiplied by 20 multiplied by 5mm
The test method comprises the following steps: the strain comprises cacao globularia (cacao) sporeBotryodiplodia theobromaeBt, Bt for short), Fusarium moniliforme (Fusarium verticillioidesFu for short), Alternaria alternata (Alternaria alternateAa for short). Referring to a test method for preventing and controlling wood mould and discoloring bacteria by using a mildew preventive in the national standard GB/T18261-2013; the sample is soaked in vacuum, the vacuum degree is kept at-0.09 MPa for 5min, the sample is placed into a culture dish which is fully coated with chromobacterium spores and hypha liquid when the sample is dried till no water drops, two glass rods are padded under the sample, and the effect is observed after the sample is cultured for 28 days in an incubator at the temperature of 28 ℃ and the humidity of 80 percent. The damage values of the test specimens are ranked in Table 4.
TABLE 4 value of damage to specimen
The control efficacy is calculated as follows: e = (1-D)1/D0) X 100, wherein E is the control efficiency (%); d1For treatment of medicaments
Average damage value of the test sample; d0Mean damage value for untreated control samples.
TABLE 5 preventive and therapeutic effects of the preparations on Chromobacterium
As can be seen from Table 5, after bamboo is treated by the preparations (the primary microemulsion type wood preservative and the secondary treatment microemulsion type wood and bamboo preservative) in the embodiments 1 to 4 of the invention, the inhibition effect on three discoloring bacteria is remarkable and is 1.20g/m2Under the condition of drug loading, although the cacao globisporus (Bt) is relatively stubborn and difficult to control, the preparations 1 and 2 still have 75 percent of control efficiency on the cacao globisporus, and exciting that the control efficiency of the preparations 3 and 4 on the Bt is as high as 100 percent; the control efficiency of 4 preparations on fusarium moniliforme (Fu) and alternaria alternate (Aa) is 100 percent.
In addition, the control efficiency of the composition on mold such as aspergillus niger, aspergillus fumigatus, trichoderma harpacum, penicillium citrinum, trichoderma viride and the like can reach 100%.
Anti-fluid loss properties of the formulation:
according to GB/T29905-2013 'test method for wood preservative loss rate', the wood is treated by liquid medicines with different concentrations, and after air drying for 21 days, an indoor water loss test is carried out. The samples are grouped and soaked in distilled water for 14 days, water is periodically changed, leachate is collected, the concentration of the medicament in the leachate is measured by HPLC, and the fixation rate of the medicament is calculated according to the GB/T29905-2013 standard.
The liquid chromatography (HPLC) conditions for azoxystrobin were as follows: the detection wavelength is 200nm, and the column temperature is 25 ℃; the sample amount is 20 mu L, and the mobile phase is a mixed solution of acetonitrile and water =60: 40; the flow rate is 0.8 mL/min, and under the conditions, the retention time of the difenoconazole is 6.93 min.
Liquid Chromatography (HPLC) conditions of kresoxim-methyl were as follows: the detection wavelength is 200nm, and the column temperature is 25 ℃; the sample amount is 20 mu L, and the mobile phase (methanol: water) =80:20 mixed solution; the flow rate is 0.8 mL/min, and under the condition, the retention time of the difenoconazole is 4.92 min
Liquid Chromatography (HPLC) conditions for pyraclostrobin were as follows: the detection wavelength is 200nm, and the column temperature is 25 ℃; the sample amount is 20 mu L, and the mobile phase is a mixed solution of (methanol: water) =75: 25; the flow rate is 1.0 mL/min, and the retention time of the difenoconazole is 7.98 min under the condition.
As can be seen from Table 6, the three agents have higher anti-leaching performance, and the fixation rates of the kresoxim-methyl and the pyraclostrobin are all more than 90% at each drug loading level. Wherein the kresoxim-methyl is 0.21 kg/m3The fixation rate under the drug-loaded water is the highest and reaches 93.4 percent, and the difference of the fixation rate under different drug-loaded levels is not obvious, so that the better anti-losing performance provides guarantee for the outdoor use of the drug.
Table 6 results of the fluid loss resistance test of the formulation-treated materials
Hydrophobic lightfastness properties of the formulation:
in the embodiments 1-4 of the invention, after the wood and bamboo are treated by the primary microemulsion type wood preservative and the secondary treatment microemulsion type wood and bamboo preservative, the hydrophobic property is good (the static contact angle is more than 150 degrees, the rolling angle is less than 5 degrees), and the hydrophobic membrane layer has good mechanical stability. The prepared wood bamboo is placed in the rhodamine B organic dye aqueous solution, and after 60-hour ultraviolet irradiation, the rhodamine B in the solution is gradually catalyzed and degraded, the solution is changed from pink to colorless, and good photocatalytic performance is shown. Has light aging resistance, the repairable super-hydrophobic wood still can keep the super-hydrophobic performance after being irradiated by Ultraviolet (UV) light for 120 h, and TiO in the coating2The nano particles can absorb and scatter ultraviolet rays, effectively inhibit the surface light degradation and light discoloration of the wood, and basically maintain the original color of the wood.
In conclusion, the invention has excellent effect on wood decay fungi, can effectively prevent and control wood discoloring fungi and mould, has good water solubility, excellent frost resistance and strong loss resistance, and has the advantages of small dosage of medicament, good stability of preparation, strong loss resistance, good hydrophobic light resistance, simple operation of method and low cost.
Claims (10)
1. The microemulsion type wood and bamboo preservative is characterized in that: the wood and bamboo preservative comprises a microemulsion type wood and bamboo preservative for primary treatment of wood and bamboo and a microemulsion type wood and bamboo preservative for secondary treatment of the wood and bamboo subjected to primary treatment;
the microemulsion type wood and bamboo preservative for primary treatment comprises the following components in percentage by weight: 0.002-0.32% of methoxyl acrylate original drug, 0.001-0.1% of insecticidal component, 0.009-1.1% of organic solvent, 0.001-0.012% of cosolvent, 0.001-0.9% of antifreeze agent, 0.007-1.2% of surfactant, 0-0.6% of penetrating agent, 0-0.3% of defoaming agent and the balance of water;
the microemulsion type wood and bamboo preservative for secondary treatment is prepared by adding 0.1-0.9 percent of polyacrylic acid and 0.1-0.9 percent of nano titanium dioxide in percentage by weight into residual liquid after wood and bamboo are treated by the microemulsion type wood and bamboo preservative for primary treatment.
2. The microemulsion type wood and bamboo preservative according to claim 1, which is characterized in that: the microemulsion type wood and bamboo preservative for primary treatment comprises the following components in percentage by weight: 0.008-0.2% of methoxyl acrylate original drug, 0.009-0.010% of insecticidal component, 0.010-1% of organic solvent, 0.009-0.01% of cosolvent, 0.009-0.7% of antifreeze agent, 0.010-1% of surfactant, 0-0.6% of penetrating agent, 0-0.3% of defoaming agent and the balance of water;
the microemulsion type wood and bamboo preservative for secondary treatment is prepared by adding 0.1-0.5 percent of polyacrylic acid and 0.1-0.5 percent of nano titanium dioxide in percentage by weight into residual liquid after wood and bamboo are treated by the microemulsion type wood and bamboo preservative for primary treatment.
3. The microemulsion type wood and bamboo preservative as claimed in claim 1 or 2, wherein the input rate of the wood and bamboo preservative in wood saplings is more than or equal to 85%, the penetration depth in the surface of bamboo chips is more than or equal to 2mm, the penetration depth in the surface of bamboo integrated materials is more than or equal to 1mm, and the application of the wood and bamboo preservative in the prevention and treatment of wood decay fungi, bamboo discoloration fungi and mold is applied to the protection of ancient building wood members.
4. The microemulsion type wood and bamboo preservative according to claim 1 or 2, characterized in that the strobilurin technical is one or more of azoxystrobin, kresoxim-methyl and pyraclostrobin;
the polyacrylic acid can be replaced by one or any combination of polyurethane, emulsified paraffin, plant tung oil and wood wax oil.
5. The microemulsion type wood and bamboo preservative according to claim 1 or 2, wherein the insecticidal component is one or more of imidacloprid, thiamethoxam, permethrin, lambda-cyhalothrin and fipronil.
6. The microemulsion type wood and bamboo preservative according to claim 1 or 2, wherein the organic solvent comprises one or more of petroleum ether, cyclohexane, dichloromethane, diethyl ether, tetrahydrofuran, cyclohexanone, acetone, methyl butanone, acetonitrile, N-methyl-formanilide, N-methyl pyrrolidone, methyl acetate, ethyl acetate, dimethyl sulfoxide, methanol, ethanol, propanol, isopropanol, polyvinyl alcohol and the like.
7. The microemulsion type wood and bamboo preservative according to claim 1 or 2, wherein the cosolvent is one or more selected from potassium iodide, benzoic acid, sodium benzoate, ethylenediamine and polyvinylpyrrolidone.
8. The microemulsion type wood and bamboo preservative according to claim 1 or 2, wherein the antifreeze is one or more selected from ethylene glycol, propylene glycol, glycerol, urea, polyethylene glycol and sorbitol.
9. The microemulsion type wood and bamboo preservative according to claim 1 or 2, wherein the surfactant is selected from one or more of the following compounds: sodium dodecyl sulfate, calcium dodecyl benzene sulfonate, polysorbate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, benzyl phenol polyoxyethylene polyoxypropylene ether, dodecyl dimethyl amine oxide, hexadecyl dimethyl ammonium oxide, didecyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, and coco trimethyl ammonium chloride;
the defoaming agent is selected from one or more of silicone oil, natural oil and fat, polyether and C12-C22 high-carbon alcohol;
the penetrating agent is selected from one or more of sodium di-sec-octyl sulfosuccinate, kerosene and azone.
10. A method for preparing the microemulsion type wood and bamboo preservative as claimed in claim 1 or 2, which comprises the following steps:
(1) the preservative for primary treatment comprises the following components in percentage by weight: 0.002-0.32% of methoxyl acrylate original drug, 0.001-0.1% of insecticidal component, 0.009-1.1% of organic solvent, 0.001-0.012% of cosolvent, 0.001-0.9% of antifreeze agent, 0.007-1.2% of surfactant, 0-0.6% of penetrating agent, 0-0.3% of defoaming agent and the balance of water;
(2) dissolving the original medicine in an organic solvent, adding a cosolvent, stirring and dissolving, adding a surfactant, an anti-freezing agent, a defoaming agent and a penetrating agent after the original medicine is completely dissolved, stirring uniformly, and adding water which is 10 times of the weight of the original medicine to prepare a primary treatment preservative;
(3) adding water which accounts for 100-1000 times of the weight of the primary treatment preservative, diluting to obtain a primary microemulsion type wood preservative, placing the primary microemulsion type wood preservative in a closed treatment tank, and carrying out vacuum pressurization treatment on a wood material in the tank, wherein the primary microemulsion type wood preservative in the tank is supposed to submerge the upper end surface of the wood material;
the wood material is radiata pine, masson pine, pinus sylvestris, douglas fir, southern pine, red pine, poplar, fir, rubber wood, bamboo wood and laminated wood thereof;
(4) vacuumizing the closed treatment tank for 10-30 min under the initial vacuum of-0.09 MPa, then pressurizing for 1-1.5 MPa for 60-120 min under the later vacuum of-0.09 MPa for 15-20 min, releasing the pressure, and collecting the residual liquid in the closed treatment tank;
(5) taking out the wood material in the closed treatment tank, and drying the wood material in a drying kiln until the water content is 12-20% to obtain a primary treatment anticorrosive wood material;
(6) adding 0.1-0.9 wt% of polyacrylic acid and 0.1-0.9 wt% of nano titanium dioxide into the collected residual liquid of the closed treatment tank, and uniformly stirring to obtain a secondary microemulsion wood preservative; the particle size of the nano titanium dioxide is 20-30 nm;
the polyacrylic acid can be replaced by one or any combination of polyurethane, emulsified paraffin, plant tung oil and wood wax oil;
(7) and (3) carrying out secondary treatment on the obtained primary-treatment anticorrosive wood material by using a secondary microemulsion type wood preservative, wherein the secondary treatment comprises the following steps:
(a) spraying the secondary microemulsion type wood preservative on the surface of the wood of the primary treatment anticorrosive wood material, uniformly spraying, naturally drying a spraying layer, then spraying the next layer, repeating for 5-8 times to obtain the treatment anticorrosive wood material;
(b) and soaking the primary-treatment anticorrosive wood material in a secondary microemulsion type wood preservative for 3-4 days, taking out the soaked wood material, and drying the soaked wood material in a drying kiln until the water content is 12-20% to obtain the treated anticorrosive wood material.
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