CN111001363A - Preparation method of high-mechanical-strength nano microcapsule with insect-trapping function - Google Patents

Abstract

Translated fromChinese

本发明公开了一种具有诱虫功能性的高机械强度纳米微胶囊的制备方法，以水为介质，传统含乙烯基小分子和含乙烯基的POSS分子为单体，油性诱虫剂为微胶囊芯材，再加入助稳定剂、乳化剂、交联剂和染料，经均质分散后，通过引发剂引发细乳液聚合生成有机/无机复合型的微胶囊。该制备方法原料经济易得，工艺较为简单，原料直接经细乳液聚合就可以直接获得目标产品，利于大面积推广应用。同时微胶囊对油性诱虫剂包埋后，可以有效起到缓释的作用，从而延长使用寿命。本发明制得的微胶囊可以与粘虫胶和塑料板均匀混合制成粘虫板，POSS基团的引入保证微胶囊不易破损，微胶囊自带染料可节省刷涂一层诱惑色来吸引昆虫的操作。

The invention discloses a preparation method of high mechanical strength nano-microcapsules with insect attracting function. Water is used as medium, traditional vinyl-containing small molecules and vinyl-containing POSS molecules are monomers, and oily insect attractants are micro-capsules. The capsule core material is added with co-stabilizers, emulsifiers, cross-linking agents and dyes, and after homogeneous dispersion, mini-emulsion polymerization is initiated by an initiator to form organic/inorganic composite microcapsules. The preparation method is economical and easy to obtain raw materials, and the process is relatively simple, and the target product can be directly obtained through the mini-emulsion polymerization of the raw materials, which is favorable for large-scale popularization and application. At the same time, the microcapsules can effectively play the role of slow release after embedding the oily insect attractant, thereby prolonging the service life. The microcapsules prepared by the invention can be uniformly mixed with the sticky shellac and plastic sheets to make sticky sticky sheets, the introduction of the POSS group ensures that the microcapsules are not easily damaged, and the microcapsules are self-contained with dyes, which can save the need of brushing a layer of tempting color to attract insects operation.

Description

Preparation method of high-mechanical-strength nano microcapsule with insect-trapping function

Technical Field

The invention relates to the field of nano material preparation, in particular to a preparation method of a high-mechanical-strength nano microcapsule with insect-trapping functionality.

Background

Food safety is always a topic closely concerned by common people and media, and the nation also provides great guarantee on the legislative level. The traditional method for killing pests and diseases mainly by pesticides is widely subject to the problem that the food safety is affected. Therefore, modern agriculture urgently needs to get rid of the traditional pest and disease damage expelling and killing mode, and a more environment-friendly method is adopted, such as a novel pest expelling and killing mode represented by a pest trapping plate, a pest trapping lamp and the like. The key core of this approach is to attract the original plant-destroying insects to the target site for killing. Therefore, the ingredients for attracting are critical, and generally speaking, the ingredients are mainly two parts, wherein the first part is the volatile oily attractant, and the other part is the specific attraction color. The oily insect attractant cannot meet the requirement of long-time use due to short exertion time, and the traditional solution is to prepare an attractant core or physically adsorb some materials, so that the problem of short volatilization time can be relieved to a certain extent, but the oily insect attractant needs to be repeatedly placed, and the release amount cannot be controlled. While the alluring color is basically achieved by painting a paint of a specific color on the base material, few materials integrate the two alluring factors.

The polymer microcapsule can effectively wrap the oily insect attractant to play a slow release role, and the release amount of the oily insect attractant can be regulated and controlled by controlling the crosslinking degree of the microcapsule. However, the conventional polymer microcapsules have a great disadvantage of insufficient strength, and are often damaged when applied to a coating or mixed with other materials to affect the use effect, so that it is necessary to enhance the overall strength of the polymer microcapsules.

Disclosure of Invention

Aiming at the technical defects, the invention aims to provide a preparation method of a high-mechanical-strength nano microcapsule with insect-trapping functionality, the prepared nano microcapsule combines an oily insect-trapping agent and trapping colors into a whole, the strength of the nano microcapsule is greatly enhanced, and the nano microcapsule plays a slow-release role in volatilization of the oily insect-trapping agent. The specific technical scheme of the invention is as follows:

a preparation method of high mechanical strength nano-microcapsule with insect-attracting function comprises the following steps: firstly, mixing and stirring 15-90mL of water, 1-10g of traditional vinyl-containing micromolecules, 1-10g of vinyl-containing POSS molecules, 0.1-5g of emulsifying agents, 0.1-5g of oily insect attractants, 0.1-5g of cross-linking agents, 0.1-3g of co-stabilizers and 0.01-1g of dyes at room temperature for 10min-1h, then treating for 1-10min at the low temperature of-10-5 ℃ through a cell crusher, adding 0.1-1g of potassium persulfate solution after the temperature is restored to the room temperature, and initiating polymerization for 5-24h at the temperature of 50-70 ℃ to finally obtain the nano microcapsule.

Wherein, the traditional vinyl-containing micromolecules are any one or a mixture of any several of ethyl methacrylate, lauryl methacrylate, butyl acrylate, styrene, acrylic acid and acrylonitrile in any proportion.

The POSS molecule containing vinyl is any one or a mixture of any several of octavinyl POSS, phenyl vinyl POSS, vinyl epoxy POSS, methyl propionyl isobutyl POSS and allyl POSS mixed in any proportion.

Wherein the emulsifier is any one or a mixture of any several of span 60, tween 80, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and dodecyl ammonium chloride mixed in any proportion.

Wherein the oily insect attractant is any one or a mixture of any several of clove oil, anethole, estolol, citral and citronellol in any proportion.

Wherein the crosslinking agent is any one or a mixture of any several of divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate and triethylene glycol dimethacrylate which are mixed in any proportion.

Wherein the co-stabilizer is any one or a mixture of any several of hexadecane, hexadecanol, vinyl silicone rubber, dodecyl mercaptan and octadecyl acrylate in any proportion.

Wherein the dye is any one or a mixture of any several of reactive yellow X-RG, lemon yellow, indigo, disperse blue E-2RL and disperse brilliant blue E-4R mixed in any proportion

Compared with the prior art, the invention has the beneficial effects that: the microcapsule preparation method adopts a miniemulsion polymerization method, and the system medium is water, so the method is green and environment-friendly. After POSS groups are introduced into the microcapsules, the mechanical strength of the microcapsules can be greatly enhanced, and the problem that the microcapsules are damaged and fail in use is avoided. After a cross-linked network structure is formed in the system, the release of the oily insect attractant can be quantitatively controlled according to the control of the cross-linking degree. The dye material is innovatively and directly introduced into the microcapsule, and the POSS group is an inorganic core consisting of a silicon-oxygen framework alternately connected by Si-O, and is a nanostructure hybrid system of polyhedral oligomeric silsesquioxane. The dyes selected by the invention are all water-soluble materials, and can not be embedded into the core material of the oil-induced insect attractant in a POSS-based microcapsule system, the physical adsorption is formed only by the mutual attraction of intermolecular force (Van der Waals force) and the wall material, and the dyes can be re-dispersed and paved on plates when being used with the pest-sticking glue material, so that the step of brushing the luring color paint on the trap plate is saved.

Drawings

FIG. 1 is a graph of the dynamic light scattering particle size analyzer of the microcapsules of example 3 of the present invention.

Detailed Description

The following examples are further detailed, but the present invention is not limited thereto, and all similar structures and similar variations thereof using the present invention shall fall within the scope of the present invention.

The invention provides a preparation method of a high-mechanical-strength nano microcapsule with insect-attracting function, which comprises the following steps: firstly, mixing and stirring 15-90mL of water, 1-10g of traditional vinyl-containing micromolecules, 1-10g of vinyl-containing POSS molecules, 0.1-5g of emulsifying agents, 0.1-5g of oily insect attractants, 0.1-5g of cross-linking agents, 0.1-3g of co-stabilizers and 0.01-1g of dyes at room temperature for 10min-1h, then treating for 1-10min at the low temperature of-10-5 ℃ through a cell crusher, adding 0.1-1g of potassium persulfate solution after the temperature is restored to the room temperature, and initiating polymerization for 5-24h at the temperature of 50-70 ℃ to finally obtain the nano microcapsule.

The traditional vinyl-containing micromolecules are any one or a mixture of any several of ethyl methacrylate, lauryl methacrylate, butyl acrylate, styrene, acrylic acid and acrylonitrile in any proportion.

The POSS molecule containing vinyl is any one or a mixture of any several of octavinyl POSS, phenyl vinyl POSS, vinyl epoxy group POSS, methyl propionyl isobutyl POSS and allyl POSS in any proportion.

The emulsifier is any one or a mixture of any several of span 60, tween 80, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and dodecyl ammonium chloride mixed in any proportion.

The oily insect attractant is any one or a mixture of any several of clove oil, anethole, estetrol, citral and citronellol in any proportion.

The cross-linking agent is any one or a mixture of any several of divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate and triethylene glycol dimethacrylate mixed in any proportion.

The co-stabilizer is any one or a mixture of any several of hexadecane, hexadecanol, vinyl silicone rubber, dodecyl mercaptan and octadecyl acrylate in any proportion.

The dye is any one or a mixture of any several of reactive yellow X-RG, lemon yellow, indigo, disperse blue E-2RL and disperse brilliant blue E-4R which are mixed in any proportion.

Example 1

50g of water, 5g of lauryl methacrylate, 1g of methylpropionyl isobutyl POSS, 0.1g of Tween 80, 0.2g of ebony alcohol, 0.1g of vinyl silicone rubber and 0.5g of active yellow X-RG are mixed and stirred at room temperature for 30min, then the mixture is treated by a cell crusher at the low temperature of-10 ℃ for 1min, the mixture is added with 0.1g of potassium persulfate aqueous solution containing an initiator after being recovered to the room temperature, the polymerization is initiated at the temperature of 60 ℃, and the nano microcapsule can be obtained after 8 h.

The microcapsule is spread on a 3cm multiplied by 3cm glass sheet, the oily insect attractant, namely the insect-attracting agent, namely the ethanol is also spread on the glass sheet, the glass sheet is placed outdoors, the microcapsule is taken back and placed into a glass bottle at intervals, the gas in the headspace with the same amount is taken after 24 hours, the concentration of the oily insect-attracting agent is detected by GC-FID, and the comparison shows that the microcapsule can maintain 67 percent of concentration after 15 days, and the concentration of the untreated oily insect-attracting agent is 0 percent. In addition, the microcapsules were not substantially damaged as observed by transmission electron microscopy after high-speed centrifugation, and represented excellent mechanical strength.

Example 2

70g of water, 8g of ethyl methacrylate, 3g of allyl POSS, 0.2g of dodecyl ammonium chloride, 1g of anethole, 0.2g of hexadecane and 0.6g of lemon yellow are mixed and stirred at room temperature for 40min, then the mixture is treated by a cell crusher at the low temperature of minus 5 ℃ for 3min, the mixture is recovered to the room temperature, then an aqueous solution containing 0.3g of initiator potassium persulfate is added to initiate polymerization at the temperature of 62 ℃, and the nano microcapsule can be obtained after 24 h.

The microcapsule is spread on a 3cm multiplied by 3cm glass sheet, the oily insect attractant anethole is also spread on the glass sheet in the same way, the glass sheet is placed outdoors, the microcapsule is taken back and placed into a glass bottle at intervals, the same amount of headspace gas is taken after 24 hours, the concentration of the oily insect attractant is detected by GC-FID, and the comparison shows that the microcapsule can maintain 32% concentration after 15 days, and the concentration of the untreated oily insect attractant is 0%. In addition, the microcapsules were not substantially damaged as observed by transmission electron microscopy after high-speed centrifugation, and represented excellent mechanical strength.

Example 3

Mixing and stirring 90g of water, 10g of butyl acrylate, 2g of vinyl epoxy group POSS, 0.3g of span 60, 2g of clove oil, 0.3g of hexadecanol and 0.7g of indigo at room temperature for 1 hour, treating for 5 minutes by a cell crusher at the low temperature of-2 ℃, returning to room temperature, adding an aqueous solution containing 0.5g of initiator potassium persulfate, and initiating polymerization at the temperature of 50 ℃ for 12 hours to obtain the nano microcapsule.

The microcapsule is spread on a 3cm multiplied by 3cm glass sheet, the same clove oil serving as the oily insect attractant is spread on the glass sheet, the glass sheet is placed outdoors, the microcapsule is taken back and placed into a glass bottle at intervals, the same amount of headspace gas is taken after 24 hours, the concentration of the oily insect attractant is detected by GC-FID, and comparison shows that the microcapsule can maintain 57% concentration after 15 days, and the concentration of the untreated oily insect attractant is 0%. In addition, the microcapsules were not substantially damaged as observed by transmission electron microscopy after high-speed centrifugation, and represented excellent mechanical strength.

As shown in FIG. 1, which is a dynamic light scattering particle size distribution Diagram (DLS) of the microcapsules prepared in example 3, the microcapsules had an average particle size of 61nm and exhibited a monodispersed distribution.

Example 4

80g of water, 6g of styrene, 4g of phenyl vinyl POSS, 1g of sodium dodecyl sulfate, 0.5g of citronellol, 1g of dodecyl mercaptan and 0.5g of disperse brilliant blue E-4R are mixed and stirred for 20min at room temperature, then the mixture is treated for 6min at the low temperature of-1 ℃ by a cell crusher, the mixture is restored to the room temperature, then 0.2g of potassium persulfate aqueous solution containing an initiator is added to initiate polymerization at the temperature of 58 ℃, and the nano microcapsule can be obtained after 6 h.

The microcapsule is spread on a 3cm multiplied by 3cm glass sheet, the oily insect attractant citronellol is also spread on the glass sheet in the same way, the glass sheet is placed outdoors, the oily insect attractant is taken back and placed into a glass bottle at intervals, the same amount of headspace gas is taken after 24 hours, the concentration of the oily insect attractant is detected by GC-FID, and the comparison shows that the microcapsule can maintain 51 percent concentration after 15 days, and the untreated oily insect attractant has 0 percent concentration. In addition, the microcapsules were not substantially damaged as observed by transmission electron microscopy after high-speed centrifugation, and represented excellent mechanical strength.

Example 5

Firstly, 65g of water, 9g of acrylonitrile, 6g of POSS containing octavinyl, 0.5g of sodium dodecyl benzene sulfonate, 3g of citral, 0.5g of octadecyl acrylate and 0.1g of disperse blue E-2RL are mixed and stirred for 50min at room temperature, then the mixture is treated for 7min by a cell crusher at the low temperature of-2 ℃, and after the mixture is recovered to the room temperature, an aqueous solution containing 0.6g of initiator potassium persulfate is added to initiate polymerization at the temperature of 70 ℃, and the nano microcapsule can be obtained after 10 h.

The microcapsule is spread on a 3cm multiplied by 3cm glass sheet, the oily insect attractant citral is also spread on the glass sheet in the same way, the glass sheet is placed outdoors, the microcapsule is taken back and placed into a glass bottle at intervals, the same amount of headspace gas is taken after 24 hours, the concentration of the oily insect attractant is detected by GC-FID, and the comparison shows that the microcapsule can maintain 35% concentration after 15 days, and the concentration of the untreated oily insect attractant is 0%. In addition, the microcapsules were not substantially damaged as observed by transmission electron microscopy after high-speed centrifugation, and represented excellent mechanical strength.

Examples	1	2	3	4	5
						Coating ratio (%)	47.2	92.1	59.8	71.3	87.4

The table above shows the coating ratios (%) of examples 1 to 5.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (8)

Translated fromChinese

1.一种具有诱虫功能性的高机械强度纳米微胶囊的制备方法，其特征在于：包括如下步骤：首先将15-90mL水、1-10g传统含乙烯基小分子、1-10g含乙烯基的POSS分子、0.1-5g乳化剂、0.1-5g油性诱虫剂、0.1-5g交联剂、0.1-3g助稳定剂和0.01-1g染料在室温条件下混合搅拌10min-1h，然后在-10-5℃低温条件下通过细胞粉碎机处理1-10min，恢复至室温后加入0.1-1g过硫酸钾溶液，在50-70℃的条件下引发聚合5-24h，最终可得所述纳米微胶囊。1. a preparation method of the high mechanical strength nano-microcapsules with insect attracting functionality, is characterized in that: comprise the steps: at first 15-90mL water, 1-10g traditional vinyl-containing small molecules, 1-10g ethylene-containing Base POSS molecule, 0.1-5g emulsifier, 0.1-5g oily insect attractant, 0.1-5g crosslinking agent, 0.1-3g co-stabilizer and 0.01-1g dye are mixed and stirred at room temperature for 10min-1h, and then in - Under the low temperature condition of 10-5 ℃, it is treated with a cell crusher for 1-10 minutes, and after returning to room temperature, 0.1-1 g of potassium persulfate solution is added, and the polymerization is initiated at 50-70 ℃ for 5-24 hours. capsule.2.根据权利要求1所述的制备方法，其特征在于：所述传统含乙烯基小分子为甲基丙烯酸乙酯、甲基丙烯酸月桂酯、丙烯酸丁酯、苯乙烯、丙烯酸、丙烯腈中的任意一种或任意几种以任意比例混合的混合物。2. preparation method according to claim 1 is characterized in that: described traditional vinyl-containing small molecule is ethyl methacrylate, lauryl methacrylate, butyl acrylate, styrene, acrylic acid, acrylonitrile in A mixture of any one or several in any proportion.3.根据权利要求1所述的制备方法，其特征在于：所述含乙烯基的POSS分子为八乙烯基POSS、苯基乙烯基POSS、乙烯基环氧基POSS、甲基丙酰异丁基POSS、烯丙基POSS中的任意一种或任意几种以任意比例混合的混合物。3. preparation method according to claim 1 is characterized in that: the POSS molecule of described vinyl group is octavinyl POSS, phenyl vinyl POSS, vinyl epoxy POSS, methyl propionyl isobutyl A mixture of any one or any of POSS and allyl POSS in any proportion.4.根据权利要求1所述的制备方法，其特征在于：所述乳化剂为司班60、吐温80、十二烷基硫酸钠、十二烷基苯磺酸钠、十二烷基氯化铵中的任意一种或任意几种以任意比例混合的混合物。4. preparation method according to claim 1, is characterized in that: described emulsifying agent is Span 60, Tween 80, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, dodecyl chloride Any one or any mixture of ammonium chlorides mixed in any proportion.5.根据权利要求1所述的制备方法，其特征在于：所述油性诱虫剂为丁香油、茴香脑、爱神木醇、柠檬醛、香茅醇中的任意一种或任意几种以任意比例混合的混合物。5. preparation method according to claim 1, is characterized in that: described oily insect attractant is any one or any several in clove oil, anethole, escarol, citral, citronellol with any Proportionally mixed mixture.6.根据权利要求1所述的制备方法，其特征在于：所述交联剂为二乙烯基苯、二甲基丙烯酸乙二醇酯、二乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯中的任意一种或任意几种以任意比例混合的混合物。6. preparation method according to claim 1 is characterized in that: described crosslinking agent is divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol A mixture of any one or any of the dimethacrylates mixed in any proportion.7.根据权利要求1所述的制备方法，其特征在于：所述助稳定剂为十六烷、十六醇、乙烯基硅橡胶、十二烷基硫醇、十八烷基丙烯酸酯中的任意一种或任意几种以任意比例混合的混合物。7. preparation method according to claim 1, is characterized in that: described auxiliary stabilizer is in hexadecane, hexadecanol, vinyl silicone rubber, dodecyl mercaptan, octadecyl acrylate A mixture of any one or several in any proportion.8.根据权利要求1所述的制备方法，其特征在于：所述染料为活性黄X-RG、柠檬黄、靛蓝、分散蓝E-2RL、分散艳蓝E-4R中的任意一种或任意几种以任意比例混合的混合物。8. preparation method according to claim 1 is characterized in that: described dyestuff is any one or any in Reactive Yellow X-RG, Tartrazine, Indigo, Disperse Blue E-2RL, Disperse Brilliant Blue E-4R Several mixtures mixed in any ratio.

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