阅读说明：本技术 一种环保无毒型的木材防腐剂的制备方法 (Preparation method of environment-friendly nontoxic wood preservative ) 是由 陈灼联 于 2021-09-22 设计创作，主要内容包括：本发明公开了一种环保无毒型的木材防腐剂的制备方法,将淀粉加入到去离子水中搅拌分散均匀,然后加入三乙胺三氟化氢和六氟磷酸铵,在室温下超声搅拌10～20min,在搅拌过程中加入淀粉酶,然后静置3～6h进行乳化,备用；将收集来的蛇床子进行粉碎,干燥后过150～200目网晒,然后将其置于浓度为75～85％的乙醇溶液中,磁力搅拌1.5～3h,置于超声循环提取机中,超声处理40～60min,过滤,收集滤液和固体物,然后用滤液对固体进行醇提6～9h,旋蒸除去溶剂,将提取固体置于真空干燥箱中80～85℃下干燥得到提取物；将改性乳化后的淀粉和提取物加入到醇类溶剂中,35～40℃下搅拌45～60min,然后加热搅拌过程中加入碱式碳酸铜和碱式碳酸锌,温度升至50～60℃继续搅拌2～4h得到防腐剂。(The invention discloses a preparation method of an environment-friendly nontoxic wood preservative, which comprises the steps of adding starch into deionized water, stirring and dispersing uniformly, then adding triethylamine hydrogen trifluoride and ammonium hexafluorophosphate, carrying out ultrasonic stirring at room temperature for 10-20 min, adding amylase in the stirring process, and then standing for 3-6 h for emulsification for later use; crushing the collected fructus cnidii, drying by a 150-200-mesh net, then placing the fructus cnidii in an ethanol solution with the concentration of 75-85%, magnetically stirring for 1.5-3 h, placing the fructus cnidii in an ultrasonic circulation extractor, carrying out ultrasonic treatment for 40-60 min, filtering, collecting filtrate and solid matters, then carrying out alcohol extraction on the solid by using the filtrate for 6-9 h, carrying out rotary evaporation to remove a solvent, and placing the extracted solid in a vacuum drying oven to be dried at the temperature of 80-85 ℃ to obtain an extract; adding the modified and emulsified starch and the extract into an alcohol solvent, stirring for 45-60 min at 35-40 ℃, then adding basic copper carbonate and basic zinc carbonate during heating and stirring, heating to 50-60 ℃, and continuing stirring for 2-4 h to obtain the preservative.)

1. The preparation method of the environment-friendly non-toxic wood preservative is characterized by comprising the following steps of:

the method comprises the following steps: adding starch into deionized water, stirring and dispersing uniformly, then adding triethylamine hydrogen trifluoride and ammonium hexafluorophosphate, performing ultrasonic stirring at room temperature for 10-20 min, adding amylase in the stirring process, and then standing for 3-6 h for emulsification for later use; wherein the mass ratio of the starch to the triethylamine trihydrofluoride to the ammonium hexafluorophosphate is (2-4): 0.42-0.65): 0.13-0.21;

step two: crushing the collected fructus cnidii, drying by a 150-200-mesh net, then placing the fructus cnidii in an ethanol solution with the concentration of 75-85%, magnetically stirring for 1.5-3 h, placing the fructus cnidii in an ultrasonic circulation extractor, carrying out ultrasonic treatment for 40-60 min, filtering, collecting filtrate and solid matters, then carrying out alcohol extraction on the solid by using the filtrate for 6-9 h, carrying out rotary evaporation to remove a solvent, and placing the extracted solid in a vacuum drying oven to be dried at the temperature of 80-85 ℃ to obtain an extract;

step three: and (3) adding the modified and emulsified starch in the step one and the extract in the step two into an alcohol solvent, stirring for 45-60 min at 35-40 ℃, then adding basic copper carbonate and basic zinc carbonate during heating and stirring, and continuously stirring for 2-4 h when the temperature is raised to 50-60 ℃ to obtain the preservative.

2. The method for preparing the environment-friendly non-toxic wood preservative according to claim 1, wherein the starch is any one of mung bean starch, tapioca starch, sweet potato starch, potato starch or corn starch.

3. The method for preparing the environment-friendly non-toxic wood preservative according to claim 1, wherein the alcohol solvent is any one of 1, 3-propanediol, 1, 2-ethanediol, 1, 4-butanediol, isoamylol and n-amyl alcohol.

4. The method for preparing an environment-friendly non-toxic wood preservative according to claim 1, wherein the mass ratio of the modified emulsified starch in the first step, the extract in the second step, the basic copper carbonate and the basic zinc carbonate is (3-4): 1.8-2.7): 0.55-0.75): 0.52-0.64.

Technical Field

The invention belongs to the technical field of preservatives, and particularly relates to a preparation method of an environment-friendly and non-toxic wood preservative.

Background

The wood is the only renewable structural material in the four materials, has the characteristics of no toxicity, no pollution, beautiful appearance, easy processing and the like, and is a green natural product which is well favored by people. However, the main components of wood are lignin, cellulose and hemicellulose, and under the condition of proper temperature, moisture, humidity and pH value, the wood is easy to be eroded and decayed by insects and bacteria, so that the service life of the wood is shortened. According to statistics, the service life of the wood subjected to preservative treatment can be prolonged by 5-6 times. Therefore, the method for performing preservative treatment on the wood is an important way and means for prolonging the service life of the wood, improving the utilization level of the wood and saving wood resources.

The wood preservative is a chemical agent, and can enhance the effects of resisting bacterial decay, insect damage, marine drilling animal erosion and the like after being injected into wood by a certain method. There are several of the following: water-borne (water-soluble) preservatives: namely a wood preservative which can be dissolved in water and takes water as a carrier. Such as CCA, ACQ, CA-B, CB-A, ACZA, ACC, CC, etc. Organic solvent (oil-borne type, oil-soluble type) preservative: a wood preservative containing pesticide, bactericide or their compound dissolved in organic solvent, such as pentachlorophenol, chlorothalonil, copper naphthenate, etc., copper 8-hydroxyquinolinate; oil preservatives: antiseptic oil, coal tar, and anthracene oil.

The wood preservatives commonly used in the world at present mainly comprise copper, chromium, arsenic (CCA), cuprammonium (ammonium) quaternary ammonium salt (ACQ), Copper Azole (CA) and the like, because the arsenic and the chromium in the CCA are toxic substances, the CCA is easy to damage human bodies, and especially when the CCA is used indoors, the CCA is more harmful to the human bodies. In the prior art, CCA has been replaced by high-efficiency and low-toxicity environment-friendly preservatives such as ACQ and CA, wood protective agents in the prior art are all prepared by adding ammonia or amine solvents into sterilization protective components, and the sterilization components and solvents (amine and ammonia) are prepared, so that ammonia or amine solvents are necessary for dissolving copper compounds and achieving sterilization protective effects, and thus, a large amount of solvents are consumed, and the amine or ammonia solvents are easy to volatilize, so that the environment is polluted.

Disclosure of Invention

Aiming at the problems that the wood protective agent in the prior art is prepared by adding ammonia or amine solvent into a sterilization protective component, the sterilization component and the solvent (amine and ammonia) are prepared, and the ammonia or amine solvent is necessary for dissolving a copper compound and achieving the sterilization protective effect, so that a large amount of solvent is consumed, and the environment is polluted because the amine or amine solvent is easy to volatilize, the invention aims to provide a preparation method of an environment-friendly and non-toxic wood preservative, which comprises the following steps:

the method comprises the following steps: adding starch into deionized water, stirring and dispersing uniformly, then adding triethylamine hydrogen trifluoride and ammonium hexafluorophosphate, performing ultrasonic stirring at room temperature for 10-20 min, adding amylase in the stirring process, and then standing for 3-6 h for emulsification for later use; wherein the mass ratio of the starch to the triethylamine trihydrofluoride to the ammonium hexafluorophosphate is (2-4): (0.42-0.65): 0.13-0.21.

Step two: crushing the collected fructus cnidii, drying by a 150-200-mesh net, then placing the fructus cnidii in 75-85% ethanol solution, magnetically stirring for 1.5-3 h, placing the fructus cnidii in an ultrasonic circulation extractor, carrying out ultrasonic treatment for 40-60 min, filtering, collecting filtrate and solid, then carrying out alcohol extraction on the solid by using the filtrate for 6-9 h, carrying out rotary evaporation to remove a solvent, and placing the extracted solid in a vacuum drying oven for drying at 80-85 ℃ to obtain the extract.

Step three: and (3) adding the modified and emulsified starch and the extract in the step (II) into an alcohol solvent, stirring for 45-60 min at 35-40 ℃, then adding basic copper carbonate and basic zinc carbonate during heating and stirring, and continuously stirring for 2-4 h when the temperature is raised to 50-60 ℃ to obtain the preservative.

Preferably, the starch is any one of mung bean starch, cassava starch, sweet potato starch, potato starch or corn starch.

Preferably, the alcohol solvent is any one of 1, 3-propanediol, 1, 2-ethanediol, 1, 4-butanediol, isoamylol and n-pentanol.

Preferably, the mass ratio of the modified emulsified starch in the first step, the extract in the second step, the basic copper carbonate and the basic zinc carbonate is (3-4): (1.8-2.7): (0.55-0.75): 0.52-0.64).

Compared with the prior art, the invention has the following beneficial effects:

according to the invention, the cnidium fruit extract is used as one of preservative raw materials, the cnidium fruit extract is compounded with modified emulsified starch, the modified emulsified starch can form a layer of protective film after wood is treated, the modified starch prepared by triethylamine, hydrogen trifluoride and ammonium hexafluorophosphate also has a preservative and antibacterial function, the cnidium fruit extract, metal salt antibacterial preservative substances, namely basic copper carbonate and basic zinc carbonate, are mutually cooperated for antibacterial and anticorrosion, the protective film formed by the modified gelatinized starch prevents external fungus substances from contacting the wood, and meanwhile, the antibacterial and antiseptic substances in the preservative can be protected from losing, so that a better preservative and antibacterial effect is achieved.

Detailed Description

The following embodiments of the present invention are described in detail, and the embodiments are implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, it should be noted that, for those skilled in the art, a plurality of modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Example 1

A preparation method of an environment-friendly nontoxic wood preservative specifically comprises the following steps:

the method comprises the following steps: adding starch into deionized water, stirring and dispersing uniformly, then adding triethylamine hydrogen trifluoride and ammonium hexafluorophosphate, performing ultrasonic stirring for 10min at room temperature, adding amylase in the stirring process, and then standing for 3h for emulsification for later use; wherein the mass ratio of the starch to the triethylamine trihydrofluoride to the ammonium hexafluorophosphate is 2:0.42: 0.13.

Step two: pulverizing collected fructus Cnidii, drying with 150 mesh net, placing into 75% ethanol solution, magnetically stirring for 1.5 hr, placing into ultrasonic circulation extractor, ultrasonic treating for 40min, filtering, collecting filtrate and solid substance, extracting solid with ethanol for 6 hr, rotary evaporating to remove solvent, and drying the solid in vacuum drying oven at 80 deg.C to obtain extract.

Step three: adding the modified and emulsified starch and the extract in the second step into a 1, 3-propylene glycol solvent, stirring for 45min at 35 ℃, then adding basic copper carbonate and basic zinc carbonate during heating and stirring, and continuously stirring for 2h when the temperature is raised to 50 ℃ to obtain the preservative; wherein the mass ratio of the modified emulsified starch in the first step, the extract in the second step, the basic copper carbonate and the basic zinc carbonate is 3:1.8:0.55: 0.52.

Example 2

A preparation method of an environment-friendly nontoxic wood preservative specifically comprises the following steps:

the method comprises the following steps: adding starch into deionized water, stirring and dispersing uniformly, then adding triethylamine hydrogen trifluoride and ammonium hexafluorophosphate, performing ultrasonic stirring at room temperature for 20min, adding amylase in the stirring process, and then standing for 6h for emulsification for later use; wherein the mass ratio of the starch to the triethylamine trihydrofluoride to the ammonium hexafluorophosphate is 4:0.65: 0.21.

Step two: pulverizing collected fructus Cnidii, drying with 200 mesh net, placing into 85% ethanol solution, magnetically stirring for 3 hr, placing into ultrasonic circulation extractor, ultrasonic treating for 60min, filtering, collecting filtrate and solid substance, extracting solid with ethanol for 9 hr, rotary steaming to remove solvent, and drying at 85 deg.C in vacuum drying oven to obtain extract.

Step three: adding the modified and emulsified starch and the extract in the second step into a 1, 2-glycol solvent, stirring for 60min at 40 ℃, then adding basic copper carbonate and basic zinc carbonate during heating and stirring, and continuously stirring for 4h when the temperature is raised to 60 ℃ to obtain the preservative; wherein the mass ratio of the modified emulsified starch in the first step, the extract in the second step, the basic copper carbonate and the basic zinc carbonate is 4:2.7:0.75: 0.64.

Example 3

A preparation method of an environment-friendly nontoxic wood preservative specifically comprises the following steps:

the method comprises the following steps: adding starch into deionized water, stirring and dispersing uniformly, then adding triethylamine hydrogen trifluoride and ammonium hexafluorophosphate, performing ultrasonic stirring for 15min at room temperature, adding amylase in the stirring process, and then standing for 5h for emulsification for later use; wherein the mass ratio of the starch to the triethylamine trihydrofluoride to the ammonium hexafluorophosphate is 3:0.58: 0.19.

Step two: pulverizing collected fructus Cnidii, drying with 180 mesh net, placing into 80% ethanol solution, magnetically stirring for 2h, placing into ultrasonic circulation extractor, ultrasonic treating for 50min, filtering, collecting filtrate and solid substance, extracting solid with ethanol for 8h, rotary steaming to remove solvent, and drying the solid in vacuum drying oven at 82 deg.C to obtain extract.

Step three: adding the modified and emulsified starch and the extract in the second step into a 1, 4-butanediol solvent, stirring for 50min at 38 ℃, then adding basic copper carbonate and basic zinc carbonate during heating and stirring, and continuously stirring for 3h when the temperature is raised to 55 ℃ to obtain the preservative; wherein the mass ratio of the modified emulsified starch in the first step, the extract in the second step, the basic copper carbonate and the basic zinc carbonate is 3.6:2.4:0.66: 0.59.

Comparative example 1

The preparation was carried out according to the method described in example two in chinese patent document CN 111844309A.

Examples of the experiments

Performance test experiment-mildew resistance test: the mildew resistance of the preservatives in examples 1-3 and comparative example 1 on wood is evaluated according to the standard GB/T18261-2013, and the test comparison standards are as follows:

grade 0, no hypha and mildew on the surface of the sample, and normal color of the interior and the exterior;

grade 1-sample surface infected area <1/4, internal color normal;

grade 2, the infected area of the surface of the sample is 1/4-1/2, and the internal color is normal;

grade 3, wherein the infection area on the surface of the sample is 1/2-3/4, or the internal color change area is < 1/10;

grade 4 — specimen surface infected area >3/4, or internal color change area > 1/10; the results are shown in Table 1 below,

table 1. mildew resistance test results:

as can be seen from Table 1, compared with the preservative prepared in comparative example 1, the preservative prepared in examples 1 to 3 of the present invention has the surface infection areas of 1/22, 1/17 and 1/20 respectively, and the test grades are all 1 grade; the surface infection area of the sample treated by the preservative and the agent in the comparative example 1 is 9/20, and the test grade is grade 2, which shows that the preservative has excellent mildew-proof effect.

Performance test 2-antibacterial performance test: sample wood was selected and prepared according to the requirements of standard GB/T13942.1-2009, and treated with the preservatives of examples 1-3 and comparative example 1 to test their antibacterial properties, the test results are shown in Table 2,

table 2. results of antibacterial testing:

as can be seen from table 2, the preservatives prepared in examples 1 to 3 of the present invention have superior antibacterial effects to those of the preservative in comparative example 1, and even after 100 days, the antibacterial effects against white rot fungi, brown rot fungi and green wood fungi are all about 92%.