CN111002415B

CN111002415B - Wood preservative and preparation method and application thereof

Info

Publication number: CN111002415B
Application number: CN201911236020.8A
Authority: CN
Inventors: 杨茜; 李甲亮; 刑岩; 魏佳楠; 郭思钰; 王明霞
Original assignee: Binzhou University
Current assignee: Binzhou University
Priority date: 2019-12-05
Filing date: 2019-12-05
Publication date: 2021-08-06
Anticipated expiration: 2039-12-05
Also published as: CN111002415A

Abstract

The invention relates to a preservative, in particular to a wood preservative and a preparation method and application thereof. The water-soluble paint consists of a component A and a component B, wherein the component A comprises metal salt, ammonia water, hydrogen peroxide, phenol, formaldehyde and oxalic acid; the component B is sodium hypochlorite; mixing the component A and the component B according to the volume ratio of 1:2-1: 10. The wood preservative has the characteristics of broad spectrum, long-acting property and quick response, the reagent is sprayed on 9cm by 9cm pine, and the bacteria on the pine can be completely disappeared after 15min observation, so that the wood preservative is low in price and has a wide development prospect.

Description

Wood preservative and preparation method and application thereof

Technical Field

The invention relates to a preservative, in particular to a wood preservative and a preparation method and application thereof.

Background

At present, wood resources in China are scarce, the consumption of wood in various industries is continuously increased, the demand for wood shows the situation of expansive development, but the wood is easily eroded by wood decay fungi in the using process, so that the waste of the wood is caused, and the use performance is reduced. Therefore, before use, wood is often required to be preserved, and there are three main types of wood preservatives on the market today: oil-based, and water-based, among which water-based wood preservatives are widely used at present because of their low cost and nonflammability. Although the first generation of water-borne wood preservatives is represented by CAA (water-soluble wood preservatives composed of three inorganic oxides of copper, chromium and arsenic or inorganic salts), and the second generation is represented by ACQ (wood preservatives composed of inorganic copper compounds and organic quaternary ammonium salt compounds), these preservatives can achieve good effects of wood preservation during use, but still have certain disadvantages:

(1) after the wood is treated by the preservative, if the wood is not subjected to harmless treatment after the service life is reached, the wood harms the ecological environment;

(2) contains heavy metals, which not only can pollute the environment, but also can cause harm to people and livestock;

(3) the permeability and the loss resistance of the wood are lower;

(4) the market price is high.

Disclosure of Invention

Aiming at the problems of low permeability and anti-leaching performance, slow effect, high cost, inconvenient use and the like in the prior art, the invention provides the wood preservative which has the characteristics of broad spectrum, long effect, quick effect, convenient use and low price; the invention also provides a preparation method, which has simple process and is easy for industrial production.

The technical scheme of the invention is as follows:

a wood preservative comprises a component A and a component B, wherein the component A comprises metal salt, ammonia water, hydrogen peroxide, phenol, formaldehyde and oxalic acid; the component B is sodium hypochlorite; mixing the component A and the component B according to the volume ratio of 1:2-1: 10.

The metal salt is one of zinc carbonate, copper sulfate, zinc chloride, copper chloride or zinc sulfate.

The component A comprises the following components in parts by weight: 7.5-9 parts of zinc carbonate, 10-30 parts of ammonia water, 7.5-9 parts of oxalic acid, 1-3 parts of hydrogen peroxide, 1-3 parts of formaldehyde and 1-3 parts of phenol.

Preferably, the a component comprises the following components by weight: 7.5 parts of zinc carbonate, 30 parts of ammonia water, 7.5 parts of oxalic acid, 1 part of hydrogen peroxide, 1 part of formaldehyde and 1 part of phenol.

The pH of the component A is 9-12. The inhibitory effect on bacteria under such alkaline conditions is best seen from the life habits of the bacteria.

Preferably, the pH of the a component is 11.

Preferably, the wood preservative of the present invention is obtained by mixing the a component and the B component in a volume ratio of 1: 8.

The invention provides a preparation method of a wood preservative, which comprises the following steps:

(1) heating oxalic acid to dissolve, cooling, adding metal salt, and adding CO₂The reaction is finished;

(2) adding ammonia water, hydrogen peroxide, formaldehyde and phenol, adjusting the pH, and stirring until the mixture is clear;

(3) sodium hypochlorite is added according to the proportion until the solution is clear and transparent.

Wherein, the heating in the step (1) is carried out to 60-80 ℃, and the cooling is carried out to 25-30 ℃.

An application of wood preservative in preventing and treating penicillium, aspergillus niger, aspergillus and brown rot on the preserved poplar and pine is disclosed.

The sodium hypochlorite has bleaching and sterilizing effects; the ammonia water, oxalic acid, hydrogen peroxide, formaldehyde and phenol are added to increase the solubility of the metal salt and play a better role in dispersion and dissolution assistance.

The preservative can effectively inhibit the growth of green flora, has an effective effect on both poplar and pine, has a more obvious preservative effect on pine, can kill bacteria within 15min, and has the advantages of short time, obvious effect, no toxicity and no harm.

The loss resistance of preservatives is mainly to investigate the water resistance of the preservative, i.e. the ability of the active ingredients of the preservative to remain in the wood for a long time without loss in water or in a humid environment. Novel wood preservative adopts laboratory water loss test method in this application, and the anti-leaching performance of new wood preservative and traditional copper-containing class wood preservative is compared, and the result shows that the fixation rate of the wood preservative that this application provided is obviously higher than traditional type preservative in timber, and the metal fixation rate under the different concentrations all is more than 90%. Tests have shown that the metal adheres strongly to the wood fibres by the action of the dispersant, preventing particle loss due to normal climatic conditions to which the treated wood may be subjected in use.

The invention has the beneficial effects that:

(1) has the characteristics of broad spectrum, long-acting property and quick response. We sprayed the reagent on 9cm by 9cm pine, and after 15min, we observed that the bacteria on the pine had completely disappeared.

(2) Low price and wide source of goods. According to the previous research of the team, the price of the preservative sold in the market at present is generally 20 rmb/kg, so that the selling price of the preservative is higher for wood suppliers, the developed preservative has sufficient sources, the price of raw materials is low, and the development prospect is wide.

(3) The formula comprises the following components in part by weight: the ammonia water, the oxalic acid, the hydrogen peroxide, the formaldehyde and the phenol play a role of a cosolvent in the formula, so that the metal salt can be better dissolved, and further metal ions are converted from a complex state into a free state, wherein the oxalic acid can convert carbonate ions in the zinc carbonate into carbon dioxide to be released.

(4) High safety and environmental protection. Has no harm to human and livestock, and does not cause pollution or damage to the environment.

(5) Is convenient to use. It is understood that the preservative in the market generally needs a pressurized penetration mode when in use, and the preservative is only sprayed (the spraying amount is 0.02 mL/cm)²) The same effect can be achieved.

(6) The preservative is clear and transparent, is faint yellow, has small damage to wood, and has unchanged mechanical strength, good texture and pleasant color after the wood is treated by the preservative.

Drawings

In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.

FIG. 1 is a graph comparing the surface flora of pine wood before and after the addition of the preservative of example 1;

FIG. 2 is a graph comparing the surface green flora of pine before and after the addition of the preservative of example 1;

FIG. 3 is a comparison of the bacterial species on the surface of poplar before and after addition of the preservative of example 1;

FIG. 4 is a graph comparing pine surface strains before and after addition of the preservative of example 1;

FIG. 5 is a comparison of poplar surface seed before and after addition of preservative of example 1.

Detailed Description

In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Examples of the experiments

First, early preparation

1. By looking up a large amount of relevant documents, the current situation and the application prospect of the wood preservative are known, and the possible microbial populations on the wood (mainly poplar and pine) are found out, wherein the main microbial populations are penicillium, aspergillus niger, aspergillus and brown rot fungi. According to the report, the substances which can possibly inhibit certain bacteria, such as zinc, copper, boron and the like, are arranged and found out, and the zinc has obvious inhibition effect on the microorganisms and can prevent the synthesis of the mildew, so that the normal growth of the organisms is influenced, and the aim of inhibiting the propagation of the microorganisms is fulfilled;

2. the composition of conventional preservatives is initially determined by a number of reviews of literature, research and discussion, concluding and summarizing the data:

(1) 0.05-0.50% of 8-hydroxyquinoline copper (Cu-8) (100% of powder) and 5.00-20.00% of glacial acetic acid (CH)₃COOH) (100% powder), Tebuconazole (TEB) (100% powder) 0.05-0.50% and Didecyl Dimethyl Ammonium Chloride (DDAC) 5.00-20.00% with the balance being water.

(2)1.5g of nano TiO₂Powder, 0.5g IPBC (3-dian 1%, 3%, 5%, 7%, 9% (with nano TiO)₂Weight ratio of aqueous suspension), titanate NDZ-105, sodium hexametaphosphate;

(3)87g of citric acid, 500g of water, 100g of basic copper carbonate, 446g of 30% ammonium hydroxide (pH 12.6);

(4) a 54g oxalic acid and 150g water

b, 100g of copper sulfate pentahydrate, 42g of 30% ammonium hydroxide, 29g of ammonium bicarbonate and 150g of water

Mixing a and b at the pH of 10.8;

(5)40g citric acid, 100g water, 100g basic copper Carbonate (CO)₂Evolution complete), 450g 30% ammonium hydroxide, pH 11.6;

(6)75g of oxalic acid, 250g of water, 75g of zinc carbonate, 200g of 30% ammonium hydroxide and pH adjustment of 12.1.

Second, the middle period is perfect

1. Continuously looking up related data to deeply understand strains existing on the wood, the defects of the preservative sold at present and the development of the preservative in the future.

2. Through the research on the components of the traditional preservative, the preservative formula for inhibiting the growth of different wood microorganisms is prepared.

Third, later use

1. Expanding the number of different wood microorganisms: firstly, preparing a culture medium (a PDA culture medium and a Chaudou culture medium); thirdly, respectively extracting different microbial bacterial sources from the existing wood, adding the different microbial bacterial sources into corresponding culture media for propagation and separation (at least 6 parallel samples of each microbial bacterial source); finally, marking the culture dish and standing in a constant temperature incubator at 30 ℃ for later use;

2. the prepared preservative is sprayed into different culture dishes, the non-sprayed preservative is used as a blank background group, meanwhile, the conventional wood preservative purchased in the market is sprayed into the same culture dish to be used as a contrast, after 2-5 days of culture, the growth condition of the microorganism in the culture dish is carefully observed, and the physiological and biochemical characteristic identification record of the microorganism is well made. As a result, the preservative provided by the merchant can eliminate the bacteria on the wood completely, but the time is long.

Example 1

The wood preservative consists of a component A and a component B, wherein the component A comprises 7.5 parts of zinc carbonate, 30 parts of ammonia water, 7.5 parts of oxalic acid, 1 part of hydrogen peroxide, 1 part of formaldehyde and 1 part of phenol, and the pH value is adjusted to 11; the component B is sodium hypochlorite; mixing the component A and the component B according to the volume ratio of 1: 8.

The preparation method comprises the following specific steps:

(1) heating oxalic acid to 80 deg.C for dissolving, cooling to 30 deg.C, adding zinc carbonate until CO is dissolved₂The reaction is finished;

(2) adding ammonia water, hydrogen peroxide, formaldehyde and phenol, adjusting the pH to 11, and stirring until the mixture is clear;

Example 2

The wood preservative consists of a component A and a component B, wherein the component A comprises 7.5 parts of zinc chloride, 30 parts of ammonia water, 7.5 parts of oxalic acid, 1 part of hydrogen peroxide, 1 part of formaldehyde and 1 part of phenol, and the pH value is adjusted to be 10; the component B is sodium hypochlorite; mixing the component A and the component B according to the volume ratio of 1: 2.

The preparation method comprises the following specific steps:

(1) heating oxalic acid to 60 deg.C for dissolving, cooling to 25 deg.C, adding zinc chloride until CO is dissolved₂The reaction is finished;

(2) adding ammonia water, hydrogen peroxide, formaldehyde and phenol, adjusting the pH value to 10, and stirring until the mixture is clear;

Example 3

The wood preservative consists of a component A and a component B, wherein the component A comprises 9 parts of copper carbonate, 20 parts of ammonia water, 7.5 parts of oxalic acid, 2 parts of hydrogen peroxide, 2 parts of formaldehyde and 3 parts of phenol, and the pH value is adjusted to 9; the component B is sodium hypochlorite; mixing the component A and the component B according to the volume ratio of 1: 8.

The preparation method comprises the following specific steps:

(1) heating oxalic acid to 70 deg.C for dissolving, cooling to 27 deg.C, adding copper carbonate until CO is obtained₂The reaction is finished;

(2) adding ammonia water, hydrogen peroxide, formaldehyde and phenol, adjusting the pH to 9, and stirring until the mixture is clear;

Example 4

The wood preservative consists of a component A and a component B, wherein the component A comprises 9 parts of copper sulfate, 20 parts of ammonia water, 7.5 parts of oxalic acid, 3 parts of hydrogen peroxide, 3 parts of formaldehyde and 3 parts of phenol, and the pH value is adjusted to 12; the component B is sodium hypochlorite; mixing the component A and the component B according to the volume ratio of 1: 10.

The preparation method comprises the following specific steps:

(1) heating oxalic acid to 70 deg.C for dissolving, cooling to 25 deg.C, adding copper sulfate, and adding CO₂The reaction is finished;

(2) adding ammonia water, hydrogen peroxide, formaldehyde and phenol, adjusting the pH value to 12, and stirring until the mixture is clear;

Comparative example 1

The preservative adopts the traditional formula as follows: copper sulfate 8 parts, ammonia water 20 parts, glacial acetic acid 10 parts, adjusting pH to 11, and adding sodium hypochlorite 1 mL.

Through example 1, the experimental results show that, as shown in fig. 1, the surface of the pine before the preservative is added is shown on the left, so that the green strains and the whitish strains are clearly seen on the surface of the pine, the pine grows in a punctate manner, and meanwhile, a light mildewed smell can be smelled. After the preservative is sprayed, the surface of the pine can be obviously seen to be smooth after 30min, no new strains grow, the two types of strains disappear before the pine surface is sprayed, and the mildew smell on the wood is also dissipated.

According to FIG. 2, the left side shows the result of culturing the pine mushrooms, which shows that large pieces of green strains grow, obvious hyphae grow in a flaky shape, and obvious mildewed odor is generated when the dish cover is opened. After 24 hours of adding the preservative, the green strains growing in the plate can be obviously seen to disappear in a large area, which shows that the preservative is very effective for inhibiting the green strains.

According to the figure 3, the left part shows the result of culturing the strains taken from the poplar wood, a plurality of green strains are grown, obvious hyphae exist, and the vessel cover is opened like villi to smell obvious mildewed smell. The results of the strains sprayed by the preservative are shown on the right, and the green and white strains basically disappear after 48 hours, which shows that the preservative formula of the invention also has good effect on the white strains.

According to FIG. 4, the left side shows the result after culturing the strain taken from pine wood, it can be seen that green strain is produced, large pieces of white hyphae are also produced, black spores are visible in the hyphae, the dish cover is opened, the old smell of mildew occurs, and the right side shows that after adding the preservative for 36h, the green and white strains basically disappear, and no new strain is produced.

According to FIG. 5, the left side shows the cultured result of the strain taken from the poplar, which shows that both white and green strains grow, and obvious hyphae exist, and the vessel cover is opened like villi to smell obvious mildewing smell. The results of the strains sprayed by the preservative are shown on the right, and the green and white strains basically disappear after 48 hours, which shows that the preservative formula of the invention also has good effect on the white strains.

Meanwhile, as can be seen from comparative example 1, the copper ions in the cosolvent or the dispersant cannot exist in a free state better, and even the alkaline environment for inhibiting the growth of bacteria cannot be optimized, the copper ions become insoluble precipitates, which is not in accordance with the green environmental protection required by people.

In conclusion, the wood preservative provided by the invention can effectively inhibit the growth of green flora, is effective on both poplar and pine, has a more obvious preservative effect on pine, can kill bacteria within 15min, and is obvious in effect, non-toxic and harmless.

Although the present invention has been described in detail by referring to the drawings in connection with the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. The wood preservative is characterized by consisting of a component A and a component B, wherein the component A comprises the following components in parts by weight: 7.5-9 parts of metal salt, 10-30 parts of ammonia water, 7.5-9 parts of oxalic acid, 1-3 parts of hydrogen peroxide, 1-3 parts of formaldehyde and 1-3 parts of phenol; and the pH of the a-component = 9-12; the component B is sodium hypochlorite; mixing the component A and the component B according to the volume ratio of 1:2-1: 10; the metal salt is one of zinc carbonate, copper sulfate, zinc chloride, copper chloride or zinc sulfate;

the wood preservative is prepared by the following preparation method:

2. The wood preservative according to claim 1, wherein the component A comprises the following components in parts by weight: 7.5 parts of metal salt, 30 parts of ammonia water, 7.5 parts of oxalic acid, 1 part of hydrogen peroxide, 1 part of formaldehyde and 1 part of phenol.

3. The wood preservative according to claim 1, characterized in that the pH of the a-component = 11.

4. The wood preservative according to claim 1, wherein the wood preservative is obtained by mixing the A component and the B component in a volume ratio of 1: 8.

5. The wood preservative according to claim 1, wherein the heating in step (1) is to 60-80 ℃ and the cooling is to 25-30 ℃.

6. Use of a wood preservative according to claim 1 for the preservation of aspen, aspergillus niger, aspergillus and brown rot fungi on aspen and pine wood.