CN108437128B

CN108437128B - Preparation method of 3-iodine-2-propynyl butyl carbamate-loaded micro-capsule type wood mildew preventive

Info

Publication number: CN108437128B
Application number: CN201810368420.3A
Authority: CN
Inventors: 李彤彤; 李冠君; 李晓文; 陆全济; 李民; 李家宁; 蒋汇川; 秦韶山; 罗微
Original assignee: Rubber Research Institute Chinese Academy Tropical Agricultural Sciences
Current assignee: Rubber Research Institute Chinese Academy Tropical Agricultural Sciences
Priority date: 2018-04-23
Filing date: 2018-04-23
Publication date: 2020-06-16
Anticipated expiration: 2038-04-23
Also published as: CN108437128A

Abstract

Provides a preparation method of a 3-iodine-2-propynyl butyl carbamate (IPBC) loaded microcapsule type wood mildew preventive and application of the microcapsule type preservative in the corrosion prevention and mildew prevention of wood and/or bamboo products. According to the invention, a solvent volatilization method is adopted, polyvinylpyrrolidone is used as a surfactant in an organic phase, tween-80 is used as an emulsifier in a water phase, and the polyvinylpyrrolidone and the emulsifier are compounded and cooperated to obtain the IPBC loaded microcapsule type wood preservative with the particle size of 40-70nm and the coating rate of more than 97%, and a wood bacteriostatic experiment shows that the IPBC loaded microcapsule type wood preservative has a good mildew-proof effect.

Description

Preparation method of 3-iodine-2-propynyl butyl carbamate-loaded micro-capsule type wood mildew preventive

Technical Field

The invention relates to the technical field of wood protection, in particular to a preparation method and application of a 3-iodine-2-propynyl butyl carbamate (IPBC) loaded microcapsule type wood mildew inhibitor.

Background

The wood is a biological material and is easy to be invaded by bacteria, insects, marine borers and other organisms. The wood preservative treatment can improve the performances of the wood such as antibiosis, insect resistance and the like, prolong the service life of the wood, and is an important way for saving wood resources and improving the utilization efficiency of the wood. The preservative effect of the preservative on wood and the harmfulness of the preservative to the environment are key performance indexes for inspecting the preservative. The early wood preservative has great harm to human beings and the environment due to components such as chromium, arsenic or sodium pentachlorophenate, and the use of the wood preservative is forbidden or strictly limited at home and abroad. With the social development, the development of novel wood preservatives with low toxicity, environmental protection and high efficiency is necessary.

The 3-iodine-2-propynyl butyl carbamate (IPBC) is a novel oil-soluble broad-spectrum bactericide, can effectively kill blue stain/mould, yeast, algae and bacteria, has special effect on fungi, has low toxicity to people and livestock, can be safely degraded, and is a high-efficiency, low-toxicity and environment-friendly green wood preservative. IPBC was used as a preservative in the us for the 20 th century and 80 s for solid wood and composites and was listed in 1998 as the AWPA standard. This has also been investigated by a number of experts, such as Musrizalmuin et al, Japan, 2003 using IPBC as a preservative and supercritical CO₂The processing method is used for carrying out antiseptic treatment on 5 structural materials, namely medium-density fiberboard, broadleaf plywood, coniferous plywood, shaving board and oriented strand board, and has good decay resistance. Domestic IPBC sterilization research is less, and Xiaozhongping et al use supercritical CO₂The fluid is used as a carrier to carry IPBC to treat fir, Chinese red pine, medium density fiberboard and particle board, the corrosion resistance of the treated material and the loss resistance of the IPBC are analyzed, and the result shows that the IPBC has better corrosion resistance effect on the pythophthora floss and the coriolus versicolor. The bactericidal effect of the iodipropynol butyl carbamate alcohol solution is researched by plum rainbow Lin and the like, and the effect that the 500mg/L IPBC alcohol solution has a shorter action on staphylococcus aureus and escherichia coli and can reach the disinfection level is demonstrated, and the resistance of the staphylococcus aureus to the IPBC alcohol solution is higher than that of the escherichia coli.

All the students directly treat wood by using IPBC as a wood preservative, but the IPBC has poor water solubility, is easy to decompose under the condition of heat or ultraviolet irradiation to lose bacteriostatic ability due to the structure of the IPBC, and generates iodine to cause yellowing of products, thereby finally influencing the quality of the products. Therefore, the improvement of the IPBC preparation and the preparation of the IPBC in a microcapsule form have important significance in improving the stability of the IPBC preparation. At present, a plurality of methods are used for preparing the microcapsules, but how to use a simple method is a key problem in obtaining the microcapsules with good stability, small and uniform granularity and high coating rate. According to the method for manufacturing the microcapsule known in the prior art, the prepared microcapsule has a large size (>100nm) and a low coating rate (< 90%), and the use of the microcapsule can cause the reduction of IPBC utilization rate, poor slow release effect and heavy environmental burden. The invention provides a microcapsule wood mildew inhibitor loaded with IPBC, which is prepared by a solvent volatilization method, and the IPBC is wrapped in a capsule wall by a microcapsule structure, so that the IPBC can be stably dispersed in water, and the light and heat stability of the IPBC can be improved. The microcapsule has uniform granularity less than 100nm, and can be directly used for treating wood. The preparation method is simple and easy to implement, and the obtained preparation has good mildew resistance.

Disclosure of Invention

The invention aims to provide a preparation method of a microcapsule type wood mildew preventive loaded with IPBC. The method is simple and convenient to operate and easy to implement, the prepared preparation has the advantages of good light and heat stability and slow release of the drug effect, and wood treated by the mildew preventive has good mildew resistance.

Therefore, the preparation method of the IPBC-loaded microcapsule type wood mildew preventive comprises the following steps:

the method comprises the following steps: adding 0.15-0.30 g of wall material into 15-30 mL of organic solvent, dissolving and stirring at the rotating speed of 1000-1200 r/min, adding 0.05-0.4 g of 3-iodine-2-propynyl butyl carbamate (IPBC) and polyvinylpyrrolidone with the mass fraction of 0.35-0.85% after complete dissolution, stirring at the rotating speed of 800-1000 r/min, and continuously stirring for 3-7 min to uniformly disperse the IPBC in the solution to form a mixed solution;

step two: adding Tween-80 with the mass fraction of 0.25-0.75% into 35-70 mL of water to form a water phase;

step three: and (3) adding the mixed solution obtained in the first step into the water phase obtained in the second step at a continuous speed under the assistance of a constant-pressure funnel, and keeping the stirring speed of the water phase at 1000-1200 r/min until the absolute ethyl alcohol is completely volatilized, so as to obtain the IPBC microcapsule type wood mildew preventive.

Preferably, the wall material comprises one or more of ethyl cellulose, chitosan, gum arabic, starch and urea resin.

Preferably, the organic solvent comprises one or more of absolute ethyl alcohol, propylene glycol, polyethylene glycol 200, polyethylene glycol 400, methanol, acetone and ethyl acetate.

The IPBC loaded microcapsule type wood mildew preventive prepared by the method is applied to corrosion prevention and mildew prevention in wood and/or bamboo products.

Preferably, the wood impregnating method is a vacuum pressurization method, the impregnating time is more than 3 hours, and the optimal time is 3-8 hours.

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

by using polyvinylpyrrolidone as a surfactant in an organic phase and tween-80 as an emulsifier in a water phase, the particle size of the microcapsule can be greatly reduced and the coating rate of the microcapsule can be improved under the compounding synergistic effect of the polyvinylpyrrolidone and the emulsifier. Through measurement, the particle size of the IPBC loaded microcapsule type wood preservative prepared by the invention is 40-70nm, and the coating rate is more than 97%. The microcapsule with the particle size reaching the nanometer level combines the high coating rate, greatly improves the activity of a single microcapsule, reduces the whole IPBC dosage, reduces the environmental burden, and has good slow release effect and lasting mildew resistance.

Drawings

FIG. 1 shows the particle size distribution of 0.3% 3-iodo-2-propynylbutylcarbamate (IPBC) microcapsules.

FIG. 2 shows the particle size distribution of 0.15% 3-iodo-2-propynylbutylcarbamate (IPBC) microcapsules.

FIG. 3 shows experimental studies on the bacteriostatic activity of wood treated with IPBC microcapsules on Trichoderma harzianum and Coccomyza cacao.

Detailed Description

Example 1. step one: adding 0.3g of ethyl cellulose into 20mL of absolute ethyl alcohol, dissolving and stirring at the rotating speed of 1200r/min, adding 0.15g of 3-iodine-2-propynyl butyl carbamate (IPBC) and polyvinylpyrrolidone with the mass fraction of 0.40% after complete dissolution, stirring at the rotating speed of 800r/min, and continuously stirring for 3min to uniformly disperse the IPBC in the solution to form a mixed solution;

step two: adding 0.25% tween-80 to 50mL of water to form an aqueous phase;

step three: and (3) adding the mixed solution obtained in the first step into the water phase obtained in the second step at a continuous speed with the help of a constant-pressure funnel, and keeping the stirring speed of the water phase at 1200r/min until the absolute ethyl alcohol is completely volatilized, so as to obtain the IPBC microcapsule type wood mildew preventive.

And (3) impregnating the prepared IPBC micro-capsule type wood mildew preventive with a wood/bamboo product. The particle size of the IPBC microcapsule prepared by adopting a laser particle sizer test is shown in figure 1, the particle size is mainly distributed in the range of 50-70nm, the coating rate of the microcapsule reaches 99%, and the antibacterial and mildewproof performance is shown in figure 3.

Example 2, step one: adding 0.20g of ethyl cellulose into 25mL of absolute ethyl alcohol, dissolving and stirring at the rotating speed of 1000r/min, adding 0.075g of 3-iodo-2-propynyl butyl carbamate (IPBC) and polyvinylpyrrolidone with the mass fraction of 0.55% after complete dissolution, stirring at the rotating speed of 800r/min, and continuously stirring for 4min to uniformly disperse the IPBC in the solution;

step two: adding 0.50% tween-80 to 50mL of water to form an aqueous phase;

step three: and (3) adding the mixed solution obtained in the first step into the water phase obtained in the second step at a continuous speed with the help of a constant-pressure funnel, and keeping the stirring speed of the water phase at 1100r/min until the absolute ethyl alcohol is completely volatilized to obtain the IPBC microcapsule type wood mildew preventive.

And (3) impregnating the prepared IPBC micro-capsule type wood mildew preventive with a wood/bamboo product. The particle size of the IPBC microcapsule prepared by adopting a laser particle sizer test is shown in figure 2, the particle size is mainly distributed in the range of 40-60nm, the coating rate of the microcapsule reaches 98%, and the antibacterial and mildewproof performance is shown in figure 3.

Example 3. step one: adding 0.25g of ethyl cellulose into 30mL of absolute ethyl alcohol, dissolving and stirring at the rotating speed of 1200r/min, adding 0.25g of 3-iodo-2-propynyl butyl carbamate (IPBC) and polyvinylpyrrolidone with the mass fraction of 0.75% after complete dissolution, stirring at the rotating speed of 900r/min, and continuously stirring for 5min to uniformly disperse the IPBC in the solution to form a mixed solution;

step two: adding 0.6% tween-80 to 45mL of water to form an aqueous phase;

step three: and (3) adding the mixed solution obtained in the first step into the water phase obtained in the second step at a continuous speed with the help of a constant pressure funnel, and keeping the stirring speed of the water phase at 1000r/min until the absolute ethyl alcohol is completely volatilized, so as to obtain the IPBC microcapsule type wood mildew preventive.

The particle size of the wood/bamboo product treated by the IPBC microcapsule type wood mildew preventive through immersion is mainly distributed in the range of 45-65nm, and the microcapsule coating rate reaches 97.5%.

Comparative example 1: essentially the same as example 1 except that in step one, no polyvinylpyrrolidone was added. The detection shows that the grain diameter of the obtained microcapsule is 0.4 micron, and the coating rate of the microcapsule is 85 percent.

Comparative example 2: essentially the same as example 1 except that in step two, polyvinyl alcohol was used in place of tween-80. The detection shows that the grain diameter of the obtained microcapsule is 0.2 micron, and the coating rate of the microcapsule is 88 percent.

Comparative example 3: essentially the same as example 1 except that in step one, sodium dodecylate was used in place of polyvinylpyrrolidone. The detection shows that the grain diameter of the obtained microcapsule is 0.25 micron, and the coating rate of the microcapsule is 86%.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims

1. A preparation method of a microcapsule type wood mildew preventive loaded with IPBC comprises the following steps:

the method comprises the following steps: adding 0.15-0.30 g of wall material into 15-30 mL of organic solvent, dissolving and stirring at the rotating speed of 1000-1200 r/min, adding 0.05-0.4 g of 3-iodine-2-propynyl butyl carbamate (IPBC) and polyvinylpyrrolidone with the mass fraction of 0.35-0.85% after complete dissolution, stirring at the rotating speed of 800-1000 r/min, and continuously stirring for 3-7 min to uniformly disperse the IPBC in the solution to form a mixed solution; wherein the organic solvent is absolute ethyl alcohol, and the wall material is ethyl cellulose;

step three: adding the mixed solution obtained in the first step into the water phase obtained in the second step at a continuous speed with the assistance of a constant pressure funnel, and keeping the stirring speed of the water phase at 1000-1200 r/min until the absolute ethyl alcohol is completely volatilized to obtain the IPBC microcapsule type wood mildew preventive;

wherein, the prepared IPBC loaded microcapsule type wood preservative has the grain diameter of 40-70nm and the coating rate of more than 97 percent.

2. Use of IPBC-loaded microencapsulated wood fungicide prepared by the process of claim 1 for the preservation and mildew prevention in wood and/or bamboo articles.

3. Use according to claim 2, wherein the IPBC microcapsule-loaded wood fungicide is applied to the wood and/or bamboo article by an impregnation method.

4. Use according to claim 3, wherein the infusion time is 3h or more.

5. Use according to claim 3, wherein the infusion process is a vacuum pressure process.