阅读说明：本技术 一种木质复合材料防霉剂的制备方法 (Preparation method of wood composite material mildew preventive ) 是由 龙礼杰 于 2019-10-10 设计创作，主要内容包括：本发明属于防霉剂制备技术领域,具体涉及一种木质复合材料防霉剂的制备方法。本发明利用三乙胺三氟化氢和六氟磷酸铵的混合溶液制备出润胀液,使油性的天然防霉液能够在木质复合材料内部深处稳定吸附,不仅在于它对木质复合材料的抑菌防霉作用,毒性较小,还能降低木质复合材料的吸水性能,此外将高钛矿渣硫酸提取的耐碱填料中重金属离子多为硫酸盐形式存在,使木质复合材料表面强度和防渗性能提高,提高了防霉剂的防潮性能和防霉效用时间；制备得到粘附剂,能够显著提高防腐液中金属离子对木质复合材料纤维的结合力,降低金属离子对人的影响,具有缓释功能,还能在碱性木质复合材料作为中和物质,降低酸性抑菌成分的损失,具有广阔的应用前景。(The invention belongs to the technical field of preparation of mildew inhibitors, and particularly relates to a preparation method of a wood composite material mildew inhibitor. The swelling liquid is prepared by using the mixed solution of triethylamine hydrogen trifluoride and ammonium hexafluorophosphate, so that the oily natural mildew-proof liquid can be stably adsorbed in the deep inside of the wood composite material, the bacteriostatic and mildew-proof effects on the wood composite material are achieved, the toxicity is low, the water absorption performance of the wood composite material can be reduced, in addition, heavy metal ions in alkali-resistant fillers extracted from the high-titanium slag sulfuric acid mostly exist in a sulfate form, the surface strength and the seepage-proof performance of the wood composite material are improved, and the moisture-proof performance and the mildew-proof effect time of the mildew-proof agent are improved; the prepared adhesive can obviously improve the binding force of metal ions in the preservative solution on wood composite fibers, reduce the influence of the metal ions on human bodies, has a slow release function, can be used as a neutralizing substance in an alkaline wood composite, reduces the loss of acidic bacteriostatic components, and has wide application prospects.)

1. A preparation method of a wood composite mildew preventive is characterized by comprising the following specific preparation steps:

mixing nano zinc oxide, nano copper oxide, shell powder and triethanolamine according to a mass ratio of 1: 2: 1, adding distilled water for dilution to obtain an antiseptic solution, mixing the antiseptic solution, a natural mildew-proof solution, an alkali-resistant filler, a swelling solution, a leaching solution and an adhesive, and stirring and dispersing to obtain a wood composite material mildew inhibitor;

the preparation method of the natural mildew-proof liquid comprises the following specific steps:

(1) mixing natural mildew-proof plant leaves and distilled water according to a mass ratio of 1: 5, grinding and dispersing for 2-3 hours to obtain a dispersion liquid, putting the dispersion liquid into a distillation flask for distillation, controlling the distillation temperature to be 90-100 ℃, distilling for 1-2 hours, removing distilled impurities, collecting to obtain a liquid fraction, adding the liquid fraction and absolute ethyl alcohol into an extraction kettle according to a mass ratio of 10: 1, inputting a supercritical carbon dioxide fluid into the extraction kettle, extracting for 45-50 minutes to obtain a supercritical fluid; (2) introducing the supercritical fluid into a rectification column for separation, controlling the pressure of the rectification column to be 6-8 MPa and the temperature to be 20-22 ℃, rectifying for 0.5-1.0 h, separating the obtained rectification liquid in a separator for 30-35 min to obtain a natural mildew-proof liquid;

the alkali-resistant filler is prepared by the following specific steps:

crushing high-titanium slag, placing the crushed high-titanium slag in a vibrating screen for screening for 30-40 min, separating and selecting the high-titanium slag with the particle size of 20-25 mu m, collecting and obtaining slag particles, mixing the obtained slag particles, 20% by mass of sulfuric acid, quicklime and distilled water according to the mass ratio of 1: 5: 1: 10, placing the mixture in a high-speed centrifuge, carrying out centrifugal treatment for 15-20 min at the rotating speed of 3000-3500 r/min, removing supernatant fluid, placing collected precipitates in a stone grinding machine for grinding for 3-4 h, and sieving by a 200-mesh sieve to obtain an alkali-resistant filler;

the leaching solution is prepared by the following steps:

putting 180-200 g of bamboo charcoal powder and 500-600 mL of 45% sodium hydroxide solution in a water bath reaction kettle with a stirrer, heating in a water bath to 60-70 ℃, starting the stirrer, stirring for 3-5 h, adjusting the pH to be neutral by using 95% glacial acetic acid, then transferring into a distillation flask, heating to 85-90 ℃, carrying out heat preservation and reflux for 2-3 h, and removing bamboo charcoal powder residues to obtain a leachate for later use;

the adhesive is prepared by the following specific steps:

adding beta-cyclodextrin and a sodium hydroxide solution with the mass fraction of 40% into a beaker, stirring for 10-15 min at room temperature, then adding 2, 3-epoxypropyltrimethylammonium chloride, placing the beaker into a water bath kettle, heating to 50-55 ℃, reacting for 3-4 h under heat preservation, and filtering to remove filtrate to obtain the adhesive.

2. The method for preparing the wood composite mildew preventive according to claim 1, wherein the wood composite mildew preventive comprises the following steps: what is needed is

The swelling liquid in the specific preparation step of the wood composite material mildew preventive is obtained by mixing triethylamine hydrogen trifluoride and ammonium hexafluorophosphate according to the mass ratio of 4: 1.

3. The method for preparing the wood composite mildew preventive according to claim 1, wherein the wood composite mildew preventive comprises the following steps: what is needed is

The mass contents of the nano zinc oxide and the nano copper oxide in the preservative solution obtained in the specific preparation step of the wood composite material mildew preventive are preferably 1-2% and 3-5%.

4. The method for preparing the wood composite mildew preventive according to claim 1, wherein the wood composite mildew preventive comprises the following steps: what is needed is

The wood composite material mildew preventive comprises, by weight, 20-22 parts of a preservative solution, 10-12 parts of a natural mildew preventive solution, 10-15 parts of an alkali-resistant filler, 50-55 parts of a swelling solution, 8-10 parts of a leaching solution and 6-7 parts of an adhesive.

5. The method for preparing the wood composite mildew preventive according to claim 1, wherein the wood composite mildew preventive comprises the following steps: what is needed is

The conditions for extracting the natural mildew-proof liquid in the specific preparation step (1) are controlled to be extraction pressure of 6-8 MPa and extraction temperature of 25-28 ℃.

6. The method for preparing the wood composite mildew preventive according to claim 1, wherein the wood composite mildew preventive comprises the following steps: the natural mildew-proof liquid is prepared by specifically preparing one of the natural mildew-proof plant leaves in the step (1) such as Chinese toon leaves, camphor leaves and thyme leaves.

7. The method for preparing the wood composite mildew preventive according to claim 1, wherein the wood composite mildew preventive comprises the following steps: the specific preparation step (2) of the natural mildew-proof liquid is that the separation pressure is controlled to be 8-10 MPa and the separation temperature is controlled to be 25-30 ℃ during separation in the separator.

8. The method for preparing the wood composite mildew preventive according to claim 1, wherein the wood composite mildew preventive comprises the following steps: the slag particles obtained in the concrete preparation step of the alkali-resistant filler, 20 mass percent of sulfuric acid, quicklime and distilled water are mixed at a mass ratio of 1: 5: 1: 10.

9. The method for preparing the wood composite mildew preventive according to claim 1, wherein the wood composite mildew preventive comprises the following steps: the adhesive is characterized in that the raw material components in the specific preparation step comprise, by weight, 70-75 parts of beta-cyclodextrin, 100-130 parts of sodium hydroxide solution with the mass fraction of 40% and 2, 3-epoxypropyltrimethylammonium chloride.

Technical Field

The invention belongs to the technical field of preparation of mildew inhibitors, and particularly relates to a preparation method of a wood composite material mildew inhibitor.

Background

The wood composite materials such as plywood, fiberboard, flakeboard and the like are endowed with good physical and mechanical properties and processability, so that the wood composite materials are paid attention and unprecedented development in various countries in the world, and are widely applied to the fields of buildings, interior decoration, automobiles and the like. However, wood composites are highly susceptible to mold, decay and worm damage caused by the harmful effects of bacteria, insects and microorganisms due to their remarkable biological properties. Especially, the areas in the south of the Yangtze river in China are high in temperature and humidity, so that the method meets the suitable conditions for the survival of the mould and is very favorable for the breeding and reproduction of the mould. Early slight mildew appears on the surface of the wood composite material and only affects the appearance, but with the development of the mildew, hyphae can penetrate into the interior of the wood composite material, decay fungi can also develop, and finally, the strength of the wood composite material is reduced, and the use value is gradually lost. Meanwhile, when a certain amount of mold spores are present in the air, allergy, asthma, etc. may occur in indoor residents or workers.

For wood composites, an effective means of mold protection remains chemical treatment. The traditional mildew preventive such as sodium pentachlorophenate and copper chromium arsenic has obvious mildew preventive effect and moderate price, but has high toxicity and great harm to people and livestock, and can cause serious environmental pollution after long-term contact or use, and the use of the mildew preventive is limited or prohibited in many countries.

The organic acid substances, ketone substances and alcohol substances contained in the environment-friendly mixed solvent such as bamboo vinegar, wood vinegar, grass vinegar and the like have the functions of expelling parasites, sterilizing and resisting bacteria and the like, and are considered as natural bacteriostats and insecticides. However, the bamboo vinegar stock solution, the wood vinegar stock solution and the grass vinegar stock solution contain water as main components, the content of active ingredients is low, the mildew-proof effect is not obvious when the bamboo vinegar stock solution, the wood vinegar stock solution and the grass vinegar stock solution are used alone, and the active ingredients are required to be enhanced. The mildew preventive greatly reduces the pollution and toxicity to human bodies and the environment, but still has the defects of large addition amount of the compound, high production cost, poor stability and the like. The invention relates to the field of building coatings, and discloses a building inorganic dry powder fiber coating for refreshing indoor air and a preparation method thereof.

In the processing process of the feed, after various grains are crushed, the nutritional ingredients of the grains are exposed in the air, and as the feed raw materials are all crops, the crops have a large amount of moulds or mould spores when being harvested, the moulds can not be killed in the processing process of the feed, when the feed is processed and stored, if the feed is not properly stored, the feed is easy to mildew, the mycotoxin content in the mildewed feed is high, a series of adverse effects can be generated on livestock and poultry, various health problems are brought to the livestock and poultry, and the most direct expression is that the feed intake of the animals is reduced; the immunization program is unchanged, the vaccine is inoculated on time, but the antibody level of the livestock and the poultry is always kept unchanged, the immunity is reduced, the production performance of the livestock and the poultry is reduced, and false return of sows is easily caused if the content of the zearalenone in the feed exceeds the standard; therefore, the feed needs to be added with a mildew preventive. Common mildewcide mainly comprises organic acid, such as propionic acid, benzoic acid, fumaric acid and the like, and has poor mildewproof effect.

The lactobacillus is a main symbiotic bacterium in the digestive tract of animals, can form a normal flora, can generate lactic acid under the condition of microaerophilic or anaerobic, has strong acid resistance, can generate one or more bacteriocins, and can effectively inhibit the growth of harmful bacteria such as bacillus subtilis, escherichia coli, staphylococcus and the like. The defect is that the heat resistance is poor, and the death rate is high under the condition of 65-75 ℃. The application is the earliest and the most extensive, and the lactic acid bacteria mainly applied at present are lactobacillus acidophilus, lactobacillus bifidus and enterococcus. The lactobacillus used as the feed additive has stronger acid production capacity so as to be beneficial to the digestion and absorption of nutrient substances in the digestive tract; the selected strains have high reproduction rate, so that the strains can quickly occupy the digestive tract; it should also have the ability to survive in the acidic environment of the stomach.

The existing mildew preventive exists: general mildew-proof effect, short effective mildew-proof time, general moisture resistance and the like.

Therefore, the invention of the excellent mildew preventive has positive significance in the technical field of preparation of the mildew preventive.

Disclosure of Invention

The invention mainly solves the technical problem, and provides a preparation method of a wood composite mildew preventive, aiming at the defects that the existing wood composite mildew preventive uses chemical agents such as sodium pentachlorophenate, copper chromium arsenic and the like as effective components, has high toxicity, can not be applied to alkaline composite wood composite materials, can react with alkaline substances to lose efficacy, is easy to absorb moisture, and shortens the effective mildew preventive time.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

a preparation method of a wood composite mildew preventive is characterized by comprising the following specific preparation steps:

mixing nano zinc oxide, nano copper oxide, shell powder and triethanolamine according to a mass ratio of 1: 2: 1, adding distilled water for dilution to obtain an antiseptic solution, mixing the antiseptic solution, a natural mildew-proof solution, an alkali-resistant filler, a swelling solution, a leaching solution and an adhesive, and stirring and dispersing to obtain a wood composite material mildew inhibitor;

the preparation method of the natural mildew-proof liquid comprises the following specific steps:

(1) mixing natural mildew-proof plant leaves and distilled water according to a mass ratio of 1: 5, grinding and dispersing for 2-3 hours to obtain a dispersion liquid, putting the dispersion liquid into a distillation flask for distillation, controlling the distillation temperature to be 90-100 ℃, distilling for 1-2 hours, removing distilled impurities, collecting to obtain a liquid fraction, adding the liquid fraction and absolute ethyl alcohol into an extraction kettle according to a mass ratio of 10: 1, inputting a supercritical carbon dioxide fluid into the extraction kettle, extracting for 45-50 minutes to obtain a supercritical fluid;

(2) introducing the supercritical fluid into a rectification column for separation, controlling the pressure of the rectification column to be 6-8 MPa and the temperature to be 20-22 ℃, rectifying for 0.5-1.0 h, separating the obtained rectification liquid in a separator for 30-35 min to obtain a natural mildew-proof liquid;

the alkali-resistant filler is prepared by the following specific steps:

crushing high-titanium slag, placing the crushed high-titanium slag in a vibrating screen for screening for 30-40 min, separating and selecting the high-titanium slag with the particle size of 20-25 mu m, collecting and obtaining slag particles, mixing the obtained slag particles, 20% by mass of sulfuric acid, quicklime and distilled water according to the mass ratio of 1: 5: 1: 10, placing the mixture in a high-speed centrifuge, carrying out centrifugal treatment for 15-20 min at the rotating speed of 3000-3500 r/min, removing supernatant fluid, placing collected precipitates in a stone grinding machine for grinding for 3-4 h, and sieving by a 200-mesh sieve to obtain an alkali-resistant filler;

the leaching solution is prepared by the following steps:

putting 180-200 g of bamboo charcoal powder and 500-600 mL of 45% sodium hydroxide solution in a water bath reaction kettle with a stirrer, heating in a water bath to 60-70 ℃, starting the stirrer, stirring for 3-5 h, adjusting the pH to be neutral by using 95% glacial acetic acid, then transferring into a distillation flask, heating to 85-90 ℃, carrying out heat preservation and reflux for 2-3 h, and removing bamboo charcoal powder residues to obtain a leachate for later use;

the adhesive is prepared by the following specific steps:

adding beta-cyclodextrin and a sodium hydroxide solution with the mass fraction of 40% into a beaker, stirring for 10-15 min at room temperature, then adding 2, 3-epoxypropyltrimethylammonium chloride, placing the beaker into a water bath kettle, heating to 50-55 ℃, reacting for 3-4 h under heat preservation, and filtering to remove filtrate to obtain the adhesive.

The swelling liquid in the specific preparation step of the wood composite material mildew preventive is obtained by mixing triethylamine hydrogen trifluoride and ammonium hexafluorophosphate according to the mass ratio of 4: 1.

The wood composite material mildew inhibitor is characterized in that the antiseptic solution obtained in the specific preparation step contains 1-2% and 3-5% of nano zinc oxide and nano copper oxide by mass.

The wood composite material mildew inhibitor comprises, by weight, 20-22 parts of a preservative solution, 10-12 parts of a natural mildew inhibitor solution, 10-15 parts of an alkali-resistant filler, 50-55 parts of a swelling solution, 8-10 parts of a leaching solution and 6-7 parts of an adhesive.

The specific preparation method of the natural mildew-proof liquid comprises the step (1) of controlling the extraction conditions to be 6-8 MPa of extraction pressure and 25-28 ℃ of extraction temperature.

The natural mildew-proof liquid is prepared by specifically preparing one of the natural mildew-proof plant leaves in the step (1) such as Chinese toon leaves, camphor leaves and thyme leaves.

The specific preparation step (2) of the natural mildew-proof liquid is that the separation pressure is controlled to be 8-10 MPa and the separation temperature is controlled to be 25-30 ℃ during separation in the separator.

The slag particles obtained in the concrete preparation step of the alkali-resistant filler, 20 mass percent of sulfuric acid, quicklime and distilled water are mixed at a mass ratio of 1: 5: 1: 10.

The adhesive is characterized in that the raw material components in the specific preparation step comprise, by weight, 70-75 parts of beta-cyclodextrin, 100-130 parts of sodium hydroxide solution with the mass fraction of 40% and 2, 3-epoxypropyltrimethylammonium chloride.

The invention has the beneficial effects that:

(1) the swelling liquid is prepared by utilizing the mixed solution of triethylamine trihydrofluoride and ammonium hexafluorophosphate, because ionized ions in the mixed solution of triethylamine trihydrofluoride and ammonium hexafluorophosphate can penetrate into an amorphous region of wood composite material fibers and reach the outer surface of a crystalline region, and swelling in the amorphous region of cellulose can be generated by destroying hydrogen bond bonding between water and cellulose, the further penetration of the mildew preventive of the wood composite material is facilitated, the electronegativity of fluorine atoms in the triethylamine trihydrofluoride and the ammonium hexafluorophosphate is large, the radius is small, and more stable hydrogen bonds can be formed with hydroxyl groups on the cellulose, so that water molecules adsorbed on the cellulose are replaced, the adsorption of the hydroxyl groups on the cellulose to the water molecules is weakened, the water molecules are easier to migrate from the inside to the outside of the wood composite material, and the oily natural mildew preventive can be stably adsorbed in the deep inside of the wood composite material, the natural mildew preventive has the effects of inhibiting bacteria and preventing mildew on the wood composite material, has low toxicity, and can form volatile nonpolar micromolecules in the wood composite material to reduce the water absorption performance of the wood composite material;

(2) the invention extracts the leachate from bamboo charcoal powder, and carries out cationic etherification on beta-cyclodextrin by using 2, 3-epoxypropyltrimethylammonium chloride to prepare the adhesive, which has excellent adhesive force on the surface of wood composite material fiber with hydroxyl, can obviously improve the binding force of metal ions in preservative solution on the wood composite material fiber, and copper ions of the wood composite material mildew preventive in the cationic etherified beta-cyclodextrin are uniformly dispersed under the cationic repulsion and are adsorbed by the electronegativity of the wood composite material fiber, so that zinc-copper bacteriostats and the like in the gel structure of the adhesive are difficult to lose, the influence of the metal ions on people is reduced, and the natural mildew preventive is stably adsorbed on the surface of the wood composite material fiber under the action of a swelling solution, therefore, the preservative and insect-proof active ingredients in the wood composite material mildew preventive have the slow release function, in addition, the bamboo charcoal powder leachate plays a role in bacteriostasis and mildew resistance, and can be used as a neutralizing substance in an alkaline wood composite material, so that the loss of acidic bacteriostasis components is reduced, and the bamboo charcoal powder leachate has a wide application prospect.

Detailed Description

Mixing natural mildew-proof plant leaves and distilled water according to a mass ratio of 1: 5, grinding and dispersing for 2-3 hours to obtain a dispersion liquid, putting the dispersion liquid into a distillation flask for distillation, controlling the distillation temperature to be 90-100 ℃, distilling for 1-2 hours, removing distilled impurities, collecting to obtain a liquid fraction, adding the liquid fraction and absolute ethyl alcohol into an extraction kettle according to a mass ratio of 10: 1, inputting a supercritical carbon dioxide fluid into the extraction kettle, extracting under the conditions that the extraction pressure is 6-8 MPa and the extraction temperature is 25-28 ℃, and extracting for 45-50 minutes to obtain a supercritical fluid, wherein the natural mildew-proof plant leaves are one of cedrela sinensis leaves, cinnamomum camphorata leaves and thyme leaves; introducing the supercritical fluid into a rectification column for separation, controlling the pressure of the rectification column to be 6-8 MPa and the temperature to be 20-22 ℃, rectifying for 0.5-1.0 h, separating the obtained rectification liquid in a separator, controlling the separation pressure to be 8-10 MPa and the separation temperature to be 25-30 ℃, and separating for 30-35 min to obtain a natural mildew-proof liquid;

crushing high-titanium slag, placing the crushed high-titanium slag in a vibrating screen for screening for 30-40 min, separating and selecting the high-titanium slag with the particle size of 20-25 mu m, collecting and obtaining slag particles, mixing the obtained slag particles, 20% by mass of sulfuric acid, quicklime and distilled water according to the mass ratio of 1: 5: 1: 10, placing the mixture in a high-speed centrifuge, carrying out centrifugal treatment for 15-20 min at the rotating speed of 3000-3500 r/min, removing supernatant fluid, placing collected precipitates in a stone grinding machine for grinding for 3-4 h, and sieving by a 200-mesh sieve to obtain an alkali-resistant filler; putting 180-200 g of bamboo charcoal powder and 500-600 mL of 45% sodium hydroxide solution in a water bath reaction kettle with a stirrer, heating in a water bath to 60-70 ℃, starting the stirrer, stirring for 3-5 h, adjusting the pH to be neutral by using 95% glacial acetic acid, then transferring into a distillation flask, heating to 85-90 ℃, carrying out heat preservation and reflux for 2-3 h, and removing bamboo charcoal powder residues to obtain a leachate for later use; adding 70-75 parts by weight of beta-cyclodextrin and 100-130 parts by weight of a 40% sodium hydroxide solution into a beaker, stirring at room temperature for 10-15 min, adding 5-10 parts by weight of 2, 3-epoxypropyltrimethylammonium chloride, placing the beaker in a water bath kettle, heating to 50-55 ℃, carrying out heat preservation reaction for 3-4 h, and filtering to remove filtrate to obtain an adhesive; mixing triethylamine trihydrofluoride and ammonium hexafluorophosphate according to a mass ratio of 4: 1 to obtain a swelling solution, mixing nano zinc oxide, nano copper oxide, shell powder and triethanolamine according to a mass ratio of 1: 2: 1, adding distilled water to dilute to obtain an anticorrosive solution, controlling the mass contents of the nano zinc oxide and the nano copper oxide in the obtained anticorrosive solution to be preferably 1-2% and 3-5%, mixing 20-22 parts of the anticorrosive solution, 10-12 parts of a natural mildew-proof solution, 10-15 parts of an alkali-resistant filler, 50-55 parts of the swelling solution, 8-10 parts of a leaching solution and 6-7 parts of an adhesive according to parts by weight, and stirring and dispersing to obtain the wood composite material mildew inhibitor.