CN104814007A - Pine moth sex pheromone microcapsule and preparation method thereof - Google Patents

Abstract

The invention relates to a pine caterpillar sex pheromone microcapsule and a preparation method thereof, and belongs to the technical field of pine caterpillar sex pheromone microcapsule embedding technology. The microcapsule includes a microcapsule wall material and a microcapsule core material, the microcapsule wall material is formed by the reaction of methyl methacrylate, methacrylic acid and an initiator to form a prepolymer liquid, and the microcapsule core material includes pine caterpillar sex pheromone and liquid paraffin , the pine caterpillar sex pheromone is cis 5, trans 7-dodecadienal, cis 5, trans 7-dodecadienol, cis 5, trans 7-dodecadienyl acetate and/or cis-5-dodecadiene acetate. The microcapsules of the present invention have the advantages of sensitivity, specificity, high efficiency, long duration, degradability, good biocompatibility, no pollution to the environment, and low price, and can be used for population monitoring and large-scale trapping and killing of pine caterpillars. Forecasting the occurrence density of the next generation of insects has good economic and ecological benefits.

Description

A kind of pine caterpillar sex pheromone microcapsule and preparation method thereof

technical field

The invention relates to a pine caterpillar sex pheromone microcapsule and a preparation method thereof. The microcapsule is used to embed the sex pheromone to achieve the purpose of prolonging the release time of the pine caterpillar sex pheromone and strengthening the mating interference and trapping of the pine caterpillar. Caterpillar sex pheromone microcapsule embedding technology technology field.

technical background

There are more than 30 species of pine caterpillars of the genus Dendrolimus (Lepidoptera: Satyridae) insects in the world, and 27 species are distributed in my country, which is the country with the most abundant types of pine caterpillars. Pine caterpillars are important forestry pests in my country, often causing immeasurable losses to pine forests. It has the advantages of many types, strong reproductive capacity, and wide distribution. Thus, the control of pine caterpillars has always been an important and thorny task in forest protection. There are many ways to prevent and control pine caterpillars, but there are certain disadvantages, such as chemical control, which can play an immediate role in the initial control, but with long-term abuse, it has a great negative impact on society and the environment . The use of insect sex pheromones to control pests is a pest control technology developed since the 1960s. Due to the advantages of high efficiency, non-toxicity, no pollution, and no harm to beneficial insects, it has been paid attention to by researchers at home and abroad. Most of the artificially synthesized insect sex pheromones are oily liquids with a special smell, which work through airflow diffusion, and are subject to degradation. In addition, they are easily affected by environmental conditions, which reduces the use effect of pheromones. This requires adding the pheromone to a suitable carrier to obtain a stable release rate, protect the active ingredients from interference, and exert the maximum biological function of the pheromone. At present, pheromone release carriers are mainly divided into solid type and liquid spray type. Solid carriers are mostly used in crops and orchards, such as rubber plugs, polyethylene tubes, polyethylene bags and hollow fibers, etc., and are also the most practically used release carriers. These release carriers have a service life of 60-140 days. Its disadvantages are It cannot maintain a stable release rate for a long time, trapping can only be effective in a short distance, and has no biodegradability, resulting in the accumulation of polymer materials in the environment and cannot be processed. These factors limit the promotion and application of solid-type release carriers, while spray-type sustained-release carriers are generally composed of degradable microemulsions, which dissolve with semiochemicals and are environmentally friendly. Such as microcapsules, paraffin carriers, etc. Among them, microcapsules are an ideal dosage form, because the preparation process of insect pheromone microcapsules is simple, and the active ingredients are enclosed in the capsule wall, which limits the diffusion of pheromones, isolates light, air and moisture, and reduces the oxidation of active ingredients. and the speed of decomposition, which can control the constant release of pheromone and maintain a long action time; at the same time, the microcapsules of sex pheromone can be applied with traditional drug application equipment, which reduces manual input and increases the speed and frequency of regulation and application. flexibility. Therefore, it is imperative to explore the microencapsulation process of sex pheromones for the pollution-free control of pine caterpillars.

Contents of the invention

The main purpose of the present invention is to overcome the problems existing in the insect sex pheromone slow-release dosage forms of the prior art, and provide a kind of stable, long-lasting pine caterpillar sex pheromone microcapsule slow-release carrier and its coating process, The microcapsule slow-release carrier prepared by the method contains pine caterpillar sex pheromones: cis 5, trans 7-dodecadienal, cis 5, trans 7-dodecadienol, cis 5, trans 7-deca Dicarbadiene acetate or cis-5-dodecadiene acetate. The population monitoring of pine caterpillars is carried out to grasp the insect situation in time, and timely take prevention and control measures to effectively prevent the outbreak of pine caterpillars. The microcapsule has the advantages of low cost, easy preparation, long-lasting effect and the like, and can be mixed with an aqueous solution to form a suspension and sprayed to attract pine caterpillars.

To achieve the above object, the present invention takes the following technical solutions:

A kind of pine caterpillar sex pheromone microcapsule, comprises microcapsule wall material and microcapsule core material, and described microcapsule wall material is the prepolymerization liquid (prepolymerization liquid) that is formed by the reaction of methyl methacrylate, methacrylic acid and initiator polymer), the microcapsule core material includes pine caterpillar sex pheromone and liquid paraffin, and the pine caterpillar sex pheromone is cis 5, trans 7-dodecadienal, cis 5, trans 7-decadienal Dicarbadienol, cis 5, trans 7-dodecadiene acetate and/or cis 5-dodecadiene acetate.

In the microcapsule wall material, the mass ratio of methyl methacrylate and methacrylic acid is 4:1; The initiator is dibenzoyl peroxide or azobisisobutyronitrile, and the usage amount of the initiator is methacrylic acid. 0.5-1% of the total mass of methyl acrylate and methacrylic acid, that is, 0.5-1% of the total amount of monomers.

The mass ratio of the microcapsule core material to the microcapsule wall material is 1:2 to 2:1, preferably 1:1, 1:2, 2:1; to obtain a yield of 30g, use a core-wall ratio of 1:1 , requires 15g of core material and 15g of wall material; according to the core-wall ratio of 1:2, 10g of core material and 20g of wall material are required; according to the core-wall ratio of 2:1, 20g of core material and 10g of wall material are required material.

In the described pine caterpillar sex pheromone microcapsules, cis 5, trans 7-dodecadienal, cis 5, trans 7-dodecadienol, cis 5, trans 7-dodecadienal The mass concentration of ester or cis-5-dodecadienyl acetate in liquid paraffin is 4-6 mg/ml, preferably 5 mg/ml.

In the described pine caterpillar sex pheromone microcapsules, preferably, the following components are included, calculated by mass concentration:

1) Cis 5, trans 7-dodecadienal, 5mg/ml. Weigh 1.0004 g of pure cis-5, trans-7-dodecadienal, and add 200 ml of liquid paraffin.

2) Cis 5, trans 7-dodecadienol, 5mg/ml. Weigh 1.0003 g of pure cis-5, trans-7-dodecadienol, and add 200 ml of liquid paraffin.

3) Cis 5, trans 7-dodecadienyl acetate, 5mg/ml. Weigh 1.0006 g of pure cis-5, trans-7-dodecadienyl acetate, and add 200 ml of liquid paraffin.

4) Cis 5-dodecadiene acetate, 5mg/ml. Weigh 1.0001 g of pure cis-5, trans-7-dodecadienyl acetate, and add 200 ml of liquid paraffin.

Among them, the above four components cis 5, trans 7-dodecadienal, cis 5, trans 7-dodecadienol, cis 5, trans 7-dodecadienyl acetate and cis 5-decadienyl The chemical purity of the dicarbadiene acetates is all greater than 90% by weight, and the purity of the stereoisomers is all greater than 80% by weight.

The preparation method of the above-mentioned pine caterpillar sex pheromone microcapsules comprises the steps of: using the prepolymer (liquid) generated by the reaction of methyl methacrylate, methacrylic acid and initiator as a mixed wall material, and the pine caterpillar sex pheromone cis 5 , trans 7-dodecadienal, cis 5, trans 7-dodecadienol, cis 5, trans 7-dodecadienyl acetate and cis 5-dodecadienyl acetate and Liquid paraffin is used as a core material, polyvinyl alcohol is used as a dispersant, and after emulsification and reaction, the white microcapsule powder is obtained by drying at low temperature.

The preparation method of the described pine caterpillar sex pheromone microcapsules comprises the following specific steps:

(1) Pre-polymerization: Add the initiator to methyl methacrylate and methacrylic acid, react in a water bath at 60-70°C for 20-40 minutes, and stir magnetically to obtain a pre-polymerization liquid;

(2) Emulsification: mix the prepolymer liquid with the microcapsule core material composed of pine caterpillar sex pheromone and liquid paraffin with polyvinyl alcohol (PVA) aqueous solution according to the ratio, and carry out shear emulsification. The essence of the emulsification process is to The process of crushing and refining aggregates into micron-sized particles to achieve the purpose of emulsifying the core material;

(3) Forming: Then the water bath is heated to about 75°C to react for 2.5-3.5 hours, washed and filtered, and finally dried at low temperature to obtain white powdery particles.

Due to the presence of a polymerization inhibitor in methyl methacrylate, it is best to refine methyl methacrylate before use. The refining method is as follows: Methyl methacrylate is washed repeatedly with sodium hydroxide until it is no longer delaminated, and then Repeatedly wash with water until it is colorless and transparent, remove the lower layer solution to obtain refined methyl methacrylate, pour it into a sample bottle (dark bottle), and set aside.

In step (1), non-stop slow stirring is required during the prepolymerization of the above-mentioned monomers, and the stirring speed is controlled at 200-300 rpm to prevent the stirring speed from being too fast or detonation without stirring to form a solid block.

In step (2), a shear emulsifier is used for shear emulsification, the shear emulsification time is 2-5 minutes, the rotational speed of shear emulsification is 9000-11000 rpm, and the emulsification temperature is 60-70°C.

The mass ratio of the emulsified oil phase composed of wall material and core material to the water phase composed of polyvinyl alcohol (PVA) aqueous solution is 1:4～1:6; The mass ratio of alcohol (PVA) aqueous solution is 1:4～1:6. The mass concentration of polyvinyl alcohol (PVA) aqueous solution is 0.1-0.2%.

Slowly drop the mixture of the emulsified phase into an aqueous solution containing 0.2% polyvinyl alcohol and disperse with high-speed stirring, so that the oil phase is uniformly dispersed in the water phase.

In step (3), the drying temperature is 20-25° C., and the drying time is 48-72 hours.

The pine caterpillar sex pheromone microcapsule powder obtained by filtering and drying needs to be dried under low temperature conditions for 2-3 days, after drying, put it into a glass bottle, cover the mouth with aluminum foil paper, tighten the bottle cap again, and set aside.

Monomer prepolymerization 1: Mix refined methyl methacrylate and methacrylic acid in a ratio of 4:1 as a wall material, and add it to a three-necked flask with a core-to-wall ratio of 1:1, that is, 12g of methyl Methyl acrylate and 3g of methacrylic acid, adding 1% of the total amount of monomer dibenzoyl peroxide or azobisisobutyronitrile, react in a water bath at 60-70°C for a certain period of time to obtain prepolymerized liquid, spare.

Monomer prepolymerization 2: Mix refined methyl methacrylate and methacrylic acid in a ratio of 4:1 as a wall material, and add it to a three-necked flask with a core-to-wall ratio of 1:2, that is, 16g of methyl Methyl acrylate and 4g of methacrylic acid, add 1% of the total amount of monomers dibenzoyl peroxide or azobisisobutyronitrile, and react for a certain period of time in a water bath at 60-70°C to obtain a prepolymer liquid, spare.

Monomer prepolymerization 3: Mix refined methyl methacrylate and methacrylic acid in a ratio of 4:1 as a wall material, and add it to a three-necked flask with a core-to-wall ratio of 2:1, that is, 8g of methyl Methyl acrylate and 2g of methacrylic acid, adding 1% of the total amount of monomer dibenzoyl peroxide or azobisisobutyronitrile, react in a water bath at 60-70°C for a certain period of time to obtain prepolymerized liquid, spare.

The pre-polymerization solution composed of methyl methacrylate, methacrylic acid and initiator is used as the mixed wall material, the pheromone of pine caterpillar and liquid paraffin are used as the core material, and the ratio of core material and wall material is 1:1; 1:2 ; 2:1, use a high-shear emulsifier, stir at 10,000 rpm at a high speed, prepolymerize at 60-70°C for a period of time, heat up to 75°C and continue to react for a period of time, filter, dry, and use an electric heating constant temperature blast drying oven to obtain microcapsules powder.

Disperse the oil phase into the water phase: After the pre-polymerization reaction is completed, add the liquid paraffinic pheromone solution with the corresponding core wall mass ratio to the pre-polymerized corresponding pre-polymerization liquid, respectively 15g, 20g, 10g, continue Stir for 3 minutes, then add the mixture to an aqueous solution containing 0.2% PVA and stir at high speed to disperse.

The volume ratio of emulsified oil phase: water phase = 1:5, then raise the temperature (water bath) to 75°C for about 3 hours.

Wash and filter, and finally dry at 25°C for 72 hours to obtain white powder particles.

In the preparation process of the pine caterpillar sex pheromone microcapsules of the present invention, the 4 components of the pine caterpillar sex pheromone are cis 5, trans 7-dodecadienal, cis 5, trans 7-dodecadienol and cis 5 , the microencapsulation yields of trans-7-dodecadiene acetate and cis-5-dodecadiene acetate were between 84.40%-96.92%, 86.31%-98.76%, 90.72%-97.64% and Between 88.99% and 99.56%, it shows that the sex pheromone of pine caterpillar can be well microencapsulated by interfacial polymerization.

In the preparation process of the pine caterpillar sex pheromone microcapsules of the present invention, the 4 components of the pine caterpillar sex pheromone are cis 5, trans 7-dodecadienal, cis 5, trans 7-dodecadienol and cis 5 , the microcapsule coating rates of trans 7-dodecadiene acetate and cis 5-dodecadiene acetate were between 87.76%-95.11%, 89.53%-96.15%, 89.94%-95.76% and Between 90.11% and 96.16%, it shows that the sex pheromone of pine caterpillar can be microencapsulated well by interfacial polymerization.

In the preparation process of the pine caterpillar sex pheromone microcapsules of the present invention, the 4 components of the pine caterpillar sex pheromone are cis 5, trans 7-dodecadienal, cis 5, trans 7-dodecadienol and cis 5 , the microcapsule retention rate of trans 7-dodecadienyl acetate and cis-5-dodecadienyl acetate is between 51%-65%. Compared with the retention rate (respectively 1.85-42.7% and 0.41%-5.96%), the microcapsule obviously prolongs the release time of the sex pheromone of the pine caterpillar.

In the preparation process of the pine caterpillar sex pheromone microcapsules of the present invention, the 4 components of the pine caterpillar sex pheromone are cis 5, trans 7-dodecadienal, cis 5, trans 7-dodecadienol and cis 5 , the microcapsules of trans 7-dodecadienyl acetate and cis 5-dodecadienyl acetate exhibited stable release rates in the room.

The pine caterpillar sex pheromone microcapsule embedding process of the present invention has the advantages of simple preparation process, easy acquisition of wall materials, and non-toxic, biodegradable, which can effectively attract pine caterpillars, and achieves the characteristics of specificity, high efficiency, and no environmental pollution. The release rate of the sex pheromone of the pine caterpillar is reduced, and the persistence period of the sex pheromone of the pine caterpillar is prolonged. The problem of unstable and volatile pine caterpillar sex pheromones in the prior art is solved, the production cost is reduced, the number and workload of changing lures are reduced, and the cost of preventing and controlling pine caterpillars is reduced.

The pine caterpillar sex pheromone microcapsule provided by the invention also has the following advantages:

1) The pine caterpillar sex pheromone microcapsules prepared by the present invention are used for monitoring and forecasting of pine caterpillars in production. The release rate of the pine caterpillar sex pheromone microcapsule is stable, the duration of effect is long, and the moth-attracting activity is highly efficient.

2) The active ingredient is enclosed in the capsule wall, which limits the diffusion of pheromones, isolates light, air and moisture, reduces the rate of oxidation and decomposition of active ingredients, and can control the constant release of pheromones and maintain a long acting time .

3) For the pine caterpillar sex pheromone microcapsules of the present invention, the purity requirements of each active ingredient are not strict, and the moth luring effect will not be poor due to the problem of purity, nor will it be due to the purity requirements for the pine caterpillar sex pheromone components. Excessively high and greatly increase the cost of prevention and treatment.

Description of drawings

Figure 1-1 to Figure 1-4 are the sex pheromones of pine caterpillars containing Z5, E7-12: OH, Z5, E7-12: OAc, Z5, E7-12: Ald or Z5-12: OAc in Example 1 respectively Optical microscopy morphology of microcapsules.

Figure 2-1 to Figure 2-4 are the sex pheromones of pine caterpillars containing Z5, E7-12: OH, Z5, E7-12: OAc, Z5, E7-12: Ald or Z5-12: OAc in the second embodiment respectively Optical microscopy morphology of microcapsules.

Figure 3-1 to Figure 3-4 are respectively the sex pheromones of the pine caterpillar containing Z5, E7-12: OH, Z5, E7-12: OAc, Z5, E7-12: Ald or Z5-12: OAc in Example 3 Optical microscopy morphology of microcapsules.

Fig. 4 is the stability curve of the pine caterpillar sex pheromone microcapsules prepared in Example 1.

Fig. 5 is the stability curve of the pine caterpillar sex pheromone microcapsules prepared in Example 2.

Fig. 6 is the stability curve of the pine caterpillar sex pheromone microcapsules prepared in Example 3.

Detailed ways

The present invention is described in detail in conjunction with examples

Methyl methacrylate should remove the polymerization inhibitor before use, and wash it repeatedly with sodium hydroxide and water until it is colorless and transparent, and put the deblocking solution into a dark bottle for later use.

Embodiment one

The synthetic method of pine caterpillar sex pheromone microcapsule is as follows:

The first pre-polymerization: the amount of methyl methacrylate and methacrylic acid that will be refined is added to the there-necked flask in the mass ratio of 4:1, is 15g altogether, adds the initiator dibenzoyl peroxide of 0.1g, in React in a water bath at 60-70°C for 30 minutes, and stir with magnetic force.

The second emulsification: the wall material 15g and the core material 15g mixture are mixed with 150g mass concentration as 0.2% polyvinyl alcohol (PVA) aqueous solution, use shearing emulsifier to shear and emulsify 3min, rotating speed is 10000rpm, the essence of the emulsification process is to The process of crushing large particles of water into micro-groups with micron-sized particles.

The core materials are respectively cis 5, trans 7-dodecadienal (Z5, E7-12: Ald), cis 5, trans 7-dodecadienol (Z5, E7-12: OH), cis 5 , trans 7-dodecadiene acetate (Z5, E7-12: OAc) or cis 5-dodecadiene acetate (Z5-12: OAc) and liquid paraffin, calculated by mass concentration:

1) Cis 5, trans 7-dodecadienal, 5mg/ml. Weigh 1.0004 g of pure cis-5, trans-7-dodecadienal, and add 200 ml of liquid paraffin.

2) Cis 5, trans 7-dodecadienol, 5mg/ml. Weigh 1.0003 g of pure cis-5, trans-7-dodecadienol, and add 200 ml of liquid paraffin.

3) Cis 5, trans 7-dodecadienyl acetate, 5mg/ml. Weigh 1.0006 g of pure cis-5, trans-7-dodecadienyl acetate, and add 200 ml of liquid paraffin.

4) Cis 5-dodecadiene acetate, 5mg/ml. Weigh 1.0001 g of pure cis-5, trans-7-dodecadienyl acetate, and add 200 ml of liquid paraffin.

Among them, the above four components cis 5, trans 7-dodecadienal, cis 5, trans 7-dodecadienol, cis 5, trans 7-dodecadienyl acetate and cis 5-decadienyl The chemical purity of the dicarbadiene acetates is all greater than 90% by weight, and the purity of the stereoisomers is all greater than 80% by weight.

The third molding: heat up (water bath) to 75°C for about 3 hours, wash and filter, and finally dry at 25°C for 72 hours to obtain white powder particles.

As shown in Figure 1-1 to Figure 1-4, the sex information of pine caterpillars containing Z5, E7-12: OH, Z5, E7-12: OAc, Z5, E7-12: Ald or Z5-12: OAc respectively Optical microscope morphology of the microcapsules. For Z5, E7-12: OH microcapsules, under the optical microscope, the distribution is dense, the shape is regular and circular, the particle size distribution is not uniform, and the degree of uniformity is moderate; for Z5, E7-12: OAc microcapsules, under the optical microscope, The distribution is sparse, the shape is regular and circular, and the particle size distribution is relatively uniform; for Z5, E7-12:Ald microcapsules, the distribution is uniform under the optical microscope, the shape is regular and circular, and the particle size distribution is relatively uniform; for Z5-12: The distribution of OAc microcapsules is too dense under the optical microscope, the shape is regular and circular, the particle size distribution is not uniform, and the degree of uniformity is moderate.

Table 1, pine caterpillar sex pheromone microcapsule yield assay results

      

Table 2, Determination results of pine caterpillar sex pheromone microcapsule encapsulation rate

      

Table 3. Determination of retention rate of pine caterpillar sex pheromone microcapsules

      

Embodiment two

The synthetic method of pine caterpillar sex pheromone microcapsule is as follows:

The first pre-polymerization: the refined methyl methacrylate and methacrylic acid are added to a three-necked flask in a mass ratio of 4:1, which is 20g, and 0.1g of the initiator dibenzoyl peroxide is added, at 60 React in a water bath at -70°C for 30 minutes, and stir with magnetic force.

The second emulsification: mix 20g of wall material and 10g of core material with 150g mass concentration of polyvinyl alcohol (PVA) aqueous solution of 0.2%, use shear emulsifier to emulsify for 3min, the rotating speed is 10000rpm, the essence of the emulsification process is to The process of crushing large particles of water into micro-groups with micron-sized particles. The composition of the core material is the same as in Example 1.

The third molding: heat up (water bath) to 75°C for about 3 hours, wash and filter, and finally dry at 25°C for 72 hours to obtain white powder particles.

As shown in Figure 2-1 to Figure 2-4, the sex information of pine caterpillars containing Z5, E7-12: OH, Z5, E7-12: OAc, Z5, E7-12: Ald or Z5-12: OAc respectively Optical microscope morphology of the microcapsules. For Z5, E7-12: OH microcapsules, the distribution is sparse under the optical microscope, the shape is irregular and circular, the particle size distribution is small, and the uniformity is not good; for Z5, E7-12: OAc microcapsules, under the optical microscope The distribution is too dense, the shape is regular and circular, and the particle size distribution is relatively small; for Z5, E7-12:Ald microcapsules, under the optical microscope, the distribution is dense, the shape is regular and circular, and the particle size distribution is not uniform and small; For Z5-12:OAc microcapsules, the distribution is too dense under the optical microscope, the shape is regular and circular, the particle size distribution is not uniform, and the uniformity is low.

Table 4, pine caterpillar sex pheromone microcapsule productive rate determination result

      

Table 5, Determination results of pine caterpillar sex pheromone microcapsule encapsulation rate

      

Table 6, pine caterpillar sex pheromone microcapsule retention rate determination result

      

Embodiment three

The synthetic method of pine caterpillar sex pheromone microcapsule is as follows:

The first pre-polymerization: the refined methyl methacrylate and methacrylic acid are added to a three-necked flask in a mass ratio of 4:1, which is 10g, and 0.1g of the initiator dibenzoyl peroxide is added, at 60 React in a water bath at -70°C for 30 minutes, and stir with magnetic force.

The second emulsification: the wall material 10g and the core material 20g mixture are mixed with 150g mass concentration as 0.2% polyvinyl alcohol (PVA) aqueous solution, use the shearing emulsifier to shear and emulsify for 3min, the rotating speed is 10000rpm, the essence of the emulsification process is to The process of crushing large particles of water into micro-groups with micron-sized particles. The composition of the core material is the same as in Example 1. The third molding: heat up (water bath) to 75°C for about 3 hours, wash and filter, and finally dry at 25°C for 72 hours to obtain white powder particles.

As shown in Figure 3-1 to Figure 3-4, the sex information of pine caterpillars containing Z5, E7-12: OH, Z5, E7-12: OAc, Z5, E7-12: Ald or Z5-12: OAc respectively Optical microscope morphology of the microcapsules. For Z5, E7-12: OH microcapsules, the distribution is uniform under the optical microscope, the shape is regular and circular, the particle size distribution is moderate, and the uniformity is excellent; for Z5, E7-12: OAc microcapsules, the distribution is moderate under the optical microscope , the shape is regular and circular, and the particle size distribution is moderate; for Z5, E7-12: Ald microcapsules, the distribution is dense under the optical microscope, the shape is regular and circular, and the particle size distribution is not uniform; for Z5-12: OAc microcapsules , under the optical microscope, the distribution is moderate, the shape is regular and circular, the particle size distribution is uniform, and the degree of uniformity is relatively high.

Table 7, pine caterpillar sex pheromone microcapsule productive rate determination result

      

Table 8, Determination results of pine caterpillar sex pheromone microcapsule encapsulation rate

      

Table 9, pine caterpillar sex pheromone microcapsule retention rate determination result

      

Embodiment Four

The pine caterpillar sex pheromone microcapsule prepared by embodiment one is carried out the mensuration of indoor release rate as follows:

The pheromones to be tested in this test include the following components, calculated by mass concentration: cis 5, trans 7-dodecadienal, 5 mg/ml; cis 5, trans 7-dodecadienol, 5 mg/ml ml; cis 5, trans 7-dodecadiene acetate, 5mg/ml; cis 5-dodecadiene acetate, 5mg/ml. The release carrier methyl methacrylate-methacrylic acid microcapsules (MMA-MAA), the core wall (mass) ratio is 1:1, and the adsorbent Porapak Q is filled into the sampling tube with 150mg/sampling tube, and the Aging at high temperature for 2 hours.

Collect the volatile odor of pheromones indoors, put the weighed different types of microcapsules into corresponding fire observation bottles, and release them with the open mouth. The indoor temperature is 24-26°C, relative humidity is 50-80%, and wind speed is 20cm/ sec. Atmospheric sampler (QC-1 type, Beijing Institute of Labor Protection Science) was connected to the sampling tube with a Teflon tube at the air inlet port, and the gas flow rate was 100ml/min for 60min. Immediately after processing, rinse with chromatographically pure n-hexane into a 4ml vial, and collect it every other day.

Using 7683B series autosampler and 7890A-GC instrument for analysis. Nitrogen was used as carrier gas, splitless injection (valve opened after 0.75 min), and the detector was a flame ionization detector (FID). Agilent Chemstation software was used for data acquisition and analysis. The chromatographic retention time was quantified by the external standard method.

The stability of the pine caterpillar sex pheromone microcapsules is shown in Figure 4. In terms of the stability of the four pine caterpillar sex pheromone components methyl methacrylate-methacrylic acid microcapsules (MMA-MAA), their release rate fluctuations are quite small, the release is stable, and the duration is long. Daily The release amount is uniform, as the release carrier of sex pheromone, it can ensure the uniform and slow release of sex pheromone, and can protect the sex pheromone components from being oxidized and decomposed by environmental factors such as air and light, and can keep the sex pheromone lasting. biological activity. Under normal conditions, the validity period of the pine caterpillar sex pheromone microcapsules is about 100 days, which can just cover the entire occurrence period of adults.

Embodiment five

The pine caterpillar sex pheromone microcapsule prepared by embodiment two is carried out the mensuration of indoor release rate as follows

The pheromones to be tested in this test include the following components, calculated by mass concentration: cis 5, trans 7-dodecadienal, 5 mg/ml; cis 5, trans 7-dodecadienol, 5 mg/ml ml; cis 5, trans 7-dodecadiene acetate, 5mg/ml; cis 5-dodecadiene acetate, 5mg/ml. The release carrier methyl methacrylate-methacrylic acid microcapsules (MMA-MAA) core wall (mass) ratio is 1:2. Adsorbent Porapak Q is filled into the sampling tube at 150mg/sampling tube and heated at 200°C before use. Conditioned aging 2h.

Collect the volatile odor of pheromones indoors, put the weighed different types of microcapsules into corresponding fire observation bottles, and release them with the open mouth. The indoor temperature is 24-26°C, relative humidity is 50-80%, and wind speed is 20cm/ sec. Atmospheric sampler (QC-1 type, Beijing Institute of Labor Protection Science) was connected to the sampling tube with a Teflon tube at the air inlet port, and the gas flow rate was 100ml/min for 60min. Immediately after processing, rinse with chromatographically pure n-hexane into a 4ml vial, and collect it every other day.

Using 7683B series autosampler and 7890A-GC instrument for analysis. Nitrogen was used as carrier gas, splitless injection (valve opened after 0.75 min), and the detector was a flame ionization detector (FID). Agilent Chemstation software was used for data acquisition and analysis. The chromatographic retention time was quantified by the external standard method.

The stability of the pine caterpillar sex pheromone microcapsules is shown in Figure 5. In terms of the stability of the four pine caterpillar sex pheromone components methyl methacrylate-methacrylic acid microcapsules (MMA-MAA), their release rate fluctuations are quite small, the release is stable, and the duration is long. Daily The release amount is uniform, as the release carrier of sex pheromone, it can ensure the uniform and slow release of sex pheromone, and can protect the sex pheromone components from being oxidized and decomposed by environmental factors such as air and light, and can keep the sex pheromone lasting. biological activity. Under normal conditions, the validity period of the pine caterpillar sex pheromone microcapsules is about 100 days, which can just cover the entire occurrence period of adults.

Embodiment six

The pine caterpillar sex pheromone microcapsule prepared by embodiment three is carried out the mensuration of indoor release rate as follows

The pheromones to be tested in this test include the following components, calculated by mass concentration: cis 5, trans 7-dodecadienal, 5 mg/ml; cis 5, trans 7-dodecadienol, 5 mg/ml ml; cis 5, trans 7-dodecadiene acetate, 5mg/ml; cis 5-dodecadiene acetate, 5mg/ml. The release carrier methyl methacrylate-methacrylic acid microcapsules (MMA-MAA), the core wall (mass) ratio is 2:1, and the adsorbent Porapak Q is filled into the sampling tube with 150mg/sampling tube, and the Aging at high temperature for 2 hours.

Collect the volatile odor of pheromones indoors, put the weighed different types of microcapsules into corresponding fire observation bottles, and release them with the open mouth. The indoor temperature is 24-26°C, relative humidity is 50-80%, and wind speed is 20cm/ sec. Atmospheric sampler (QC-1 type, Beijing Institute of Labor Protection Science) was connected to the sampling tube with a Teflon tube at the air inlet port, and the gas flow rate was 100ml/min for 60min. Immediately after processing, rinse with chromatographically pure n-hexane into a 4ml vial, and collect it every other day.

Using 7683B series autosampler and 7890A-GC instrument for analysis. Nitrogen was used as carrier gas, splitless injection (valve opened after 0.75 min), and the detector was a flame ionization detector (FID). Agilent Chemstation software was used for data acquisition and analysis. The chromatographic retention time was quantified by the external standard method.

The stability of the pine caterpillar sex pheromone microcapsules is shown in Figure 6. In terms of the stability of the four pine caterpillar sex pheromone components methyl methacrylate-methacrylic acid microcapsules (MMA-MAA), their release rate fluctuations are quite small, the release is stable, and the duration is long. Daily The release amount is uniform, as the release carrier of sex pheromone, it can ensure the uniform and slow release of sex pheromone, and can protect the sex pheromone components from being oxidized and decomposed by environmental factors such as air and light, and can keep the sex pheromone lasting. biological activity. Under normal conditions, the validity period of the pine caterpillar sex pheromone microcapsules is about 100 days, which can just cover the entire occurrence period of adults.

In the pine caterpillar sex pheromone microcapsules of the present invention, the sex pheromone comprises the following components: cis 5, trans 7-dodecadienal, cis 5, trans 7-dodecadienol, cis 5, trans 7-dodecadiene acetate and cis-5-dodecadiene acetate. The prepared attractant adopts the interfacial polymerization method, using methyl methacrylate and methacrylic acid as the mixed wall material, benzoyl peroxide or azobisisobutyronitrile as the initiator, and polyvinyl alcohol (PVC) as the The dispersant prepared the pine caterpillar sex pheromone microcapsules. The microcapsules of the present invention have the advantages of sensitivity, specificity, high efficiency, long duration, degradability, good biocompatibility, no pollution to the environment, and low price, and can be used for population monitoring and large-scale trapping and killing of pine caterpillars. Forecasting the occurrence density of the next generation of insects has good economic and ecological benefits.

Claims (10)

1. pine moth pheromone microcapsules, it is characterized in that: comprise microcapsule wall material and microcapsules core, described microcapsule wall material is the pre-polymerization liquid formed by methyl methacrylate, methacrylic acid and initiator for reaction, described microcapsules core comprises pine moth pheromone and atoleine, described pine moth pheromone is along 5, anti-7-12 carbon two olefine aldehydr, suitable 5, anti-7-Pherocon CM, suitable 5, anti-7-12 carbon diene acetic acid esters and/or suitable 5-12 carbon diene acetic acid esters.

2. pine moth pheromone microcapsules according to claim 1, is characterized in that: the mass ratio of methyl methacrylate and methacrylic acid is 4:1; Described initator is dibenzoyl peroxide or azodiisobutyronitrile, and the usage amount of initator is 0.5 ~ 1% of methyl methacrylate and methacrylic acid gross mass.

3. pine moth pheromone microcapsules according to claim 1, is characterized in that: described microcapsules core and the mass ratio of microcapsule wall material are 1:2 ~ 2:1.

4. pine moth pheromone microcapsules according to claim 1, it is characterized in that: in described pine moth pheromone microcapsules, along 5, anti-7-12 carbon two olefine aldehydr, suitable 5, anti-7-Pherocon CM, suitable 5, anti-7-12 carbon diene acetic acid esters and/or the suitable mass concentration of 5-12 carbon diene acetic acid esters in atoleine are 4 ~ 6mg/ml.

5. pine moth pheromone microcapsules according to claim 4, it is characterized in that: along 5, anti-7-12 carbon two olefine aldehydr, suitable 5, anti-7-Pherocon CM, suitable 5, the chemical purity of anti-7-12 carbon diene acetic acid esters and suitable 5-12 carbon diene acetic acid esters is all greater than 90 % by weight, and the purity of stereoisomer is all greater than 80 % by weight.

6. the preparation method of the pine moth pheromone microcapsules according to any one of claim 1-5, comprise the steps: using the performed polymer of methyl methacrylate, methacrylic acid and initiator for reaction generation as mixing wall material, pine moth pheromone is along 5, anti-7-12 carbon two olefine aldehydr, suitable 5, anti-7-Pherocon CM, suitable 5, anti-7-12 carbon diene acetic acid esters and along 5-12 carbon diene acetic acid esters and atoleine as core, polyvinyl alcohol is as dispersant, after Over emulsfication and reaction, low temperature drying obtains white microcapsule powder.

7. the preparation method of pine moth pheromone microcapsules according to claim 6, is characterized in that: the method comprises following steps:

(1) pre-polymerization: initator is joined in methyl methacrylate and methacrylic acid, in the water-bath of 60-70 DEG C, react 20 ~ 40min, magnetic agitation, obtains pre-polymerization liquid;

(2) emulsification: proportionally by pre-polymerization liquid and the microcapsules core be made up of pine moth pheromone and atoleine, mix with polyvinyl alcohol water solution, carry out emulsification pretreatment;

(3) shaping: then warming-in-water to 75 DEG C reaction 2.5 ~ 3.5h, washing and filtering, last low temperature drying, obtains white powder particle.

8. the preparation method of pine moth pheromone microcapsules according to claim 7, it is characterized in that: before use methyl methacrylate is refined, methyl methacrylate sodium hydroxide is cleaned repeatedly, until no longer layering, then repeatedly clean to water white transparency with clear water, except sub-cloud solution, obtain the methyl methacrylate refined.

9. the preparation method of pine moth pheromone microcapsules according to claim 6, it is characterized in that: adopt emulsification pretreatment machine to carry out emulsification pretreatment, the emulsification pretreatment time is 2 ~ 5min, and the rotating speed of emulsification pretreatment is 9000 ~ 11000rpm, and emulsifying temperature is 60-70 DEG C.

10. the preparation method of pine moth pheromone microcapsules according to claim 6, is characterized in that: the mass ratio of the aqueous phase that the emulsification oil phase of wall material and core composition and polyvinyl alcohol water solution form is 1:4 ~ 1:6; The mass concentration of polyvinyl alcohol water solution is 0.1 ~ 0.2%; Described baking temperature is 20 ~ 25 DEG C, and drying time is 48 ~ 72h.