CN113321825B - Humic acid type bird repellent pheromone core-shell structure gel and preparation method thereof - Google Patents

Humic acid type bird repellent pheromone core-shell structure gel and preparation method thereof Download PDF

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CN113321825B
CN113321825B CN202110595318.9A CN202110595318A CN113321825B CN 113321825 B CN113321825 B CN 113321825B CN 202110595318 A CN202110595318 A CN 202110595318A CN 113321825 B CN113321825 B CN 113321825B
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pheromone
shell structure
humic acid
core
repelling
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CN113321825A (en
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宋洁
陈莉君
牛育华
李龙
韩家旋
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
    • A01M29/00—Scaring or repelling devices, e.g. bird-scaring apparatus
    • A01M29/12—Scaring or repelling devices, e.g. bird-scaring apparatus using odoriferous substances, e.g. aromas, pheromones or chemical agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/04—Acids; Metal salts or ammonium salts thereof
    • C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/52—Amides or imides
    • C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F120/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2397/00—Characterised by the use of lignin-containing materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/08—Cellulose derivatives
    • C08J2401/26—Cellulose ethers
    • C08J2401/28—Alkyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24—Homopolymers or copolymers of amides or imides
    • C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide

Abstract

The invention provides humic acid type bird repelling pheromone core-shell structure gel and a preparation method thereof, wherein the humic acid type bird repelling pheromone core-shell structure gel comprises the following raw materials in parts by mass: 10-15 parts of humate, 9-10 parts of cellulose, 6-8 parts of hydrophilic monomer, 1-4 parts of bird repelling pheromone, 2-6 parts of emulsifier, 0.4-0.8 part of initiator and 0.1-0.2 part of cross-linking agent. Dissolving humate and cellulose in water, adding a hydrophilic monomer, a bird repelling pheromone, an initiator and a cross-linking agent, carrying out a cross-linking reaction, and adding an emulsifier under stirring to carry out an emulsion reaction to obtain the water-in-oil type core-shell structure bird repelling gel. The invention relieves the harm of chemical pesticide to the environment, and slowly and durably releases the bird-repelling components, thereby achieving the aim of repelling birds.

Description

Humic acid type bird-repelling pheromone core-shell structure gel and preparation method thereof
Technical Field
The invention belongs to the technical field of agricultural application, and particularly relates to humic acid type bird repellent pheromone core-shell structure gel and a preparation method thereof.
Background
The existing bird repellents are mostly chemical pesticide type, and a large amount of the bird repellents are used, so that the bird repellents poison birds and seriously pollute the environment. Due to the improvement of ecological environment, the enhancement of the protection consciousness of people on birds and the improvement of natural and humanistic environment, the number of birds is increased year by year, but the problems that the birds in orchards and paddy fields are seriously damaged, and how to drive the birds without influencing the survival of the birds and the driving without damaging the birds become problems to be solved urgently.
The core-shell structure coated drug can ensure the loading capacity of the drug, can keep the lasting drug effect and can regulate the biodegradability of the carrier. At present, drug-loaded nanoparticles exist, can achieve the purpose of slowly releasing drugs, but have single effect and short slow release time.
Disclosure of Invention
The invention aims to provide humic acid type bird-repelling pheromone core-shell structure gel and a preparation method thereof, which are used for relieving the harm of chemical pesticide on the environment, and slowly and durably releasing bird-repelling components to achieve the aim of repelling birds.
The invention is realized by adopting the following method:
a humic acid type bird repellent pheromone core-shell structure gel comprises the following raw materials in parts by weight: 10-15 parts of humate, 9-10 parts of cellulose, 6-8 parts of hydrophilic monomer, 1-4 parts of bird repelling pheromone, 2-6 parts of emulsifier, 0.4-0.8 part of initiator and 0.1-0.2 part of cross-linking agent.
Preferably, the humate is prepared from weathered coal, lignite or peat.
Preferably, the cellulose is one of carboxymethyl cellulose, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose, ethyl cellulose and hydroxyethyl cellulose.
Preferably, the hydrophilic monomer is one of acrylic acid, acrylamide and acrylonitrile.
Preferably, the bird-repelling pheromone substance is one or more of methyl anthranilate, cinnamamide, cinnamaldehyde, menthol and camphor.
Preferably, the emulsifier is span 20, span 40, span 60, tween 20, tween 60, tween 80, liquid paraffin and NaHSO3One or more of them.
Preferably, the initiator is persulfate.
Preferably, the crosslinking agent is N, N-methylenebisacrylamide.
The preparation method of the humic acid type bird repelling pheromone core-shell structure gel comprises the steps of dissolving humic acid salt and cellulose in water, adding a hydrophilic monomer, a bird repelling pheromone, an initiator and a cross-linking agent, carrying out a cross-linking reaction, and adding an emulsifier under stirring conditions to carry out an emulsion reaction to obtain the water-in-oil type core-shell structure bird repelling gel.
Preferably, the method specifically comprises the following steps:
1) dissolving humic acid in a strong base solution with the pH value of 11-14 to obtain a humate solution, and mixing the humate solution with a cellulose aqueous solution to obtain a mixed solution 1;
2) adding a hydrophilic monomer into the mixed solution 1, and adjusting the pH value to 8-9 to obtain a mixed solution 2;
3) adding the bird-repelling pheromone, the initiator and the cross-linking agent into the mixed solution 2, heating to 60-70 ℃, and carrying out cross-linking reaction for 1-2 hours to obtain a reaction solution 1;
4) adding an emulsifier into the reaction solution 1 under the condition of high-speed stirring for emulsification, and reacting to obtain the water-in-oil type core-shell structure bird-repelling gel;
5) and (3) washing the water-in-oil type core-shell structure bird repelling gel with ethyl acetate, absolute ethyl alcohol and distilled water for 3-5 times respectively, and drying to obtain humic acid type bird repelling pheromone core-shell structure gel.
Compared with the existing product, the invention has the following effects:
the invention discloses humic acid type bird-repelling pheromone core-shell structure gel which takes humic acid salt, cellulose and bird-repelling pheromone as main raw materials. Humic acid and bird-repelling pheromone are combined with the gel of the core-shell structure, the humic acid and the bird-repelling pheromone are bonded through chemical bonds, the humic acid is a high-activity substance and has multiple functional groups, the decomposition of the bird-repelling pheromone is reduced through the reaction between the functional groups, the larger the using amount of the humic acid is, the slower the decomposition speed of the bird-repelling pheromone is, meanwhile, the bird-repelling pheromone is loaded into the core-shell structure by utilizing the structural characteristics of the gel, the gel slowly and durably releases bird-repelling components, and the shell layer plays a role in protecting the core layer, so that the rapid decomposition phenomenon of the bird-repelling pheromone is further reduced, the medicament can play a role in high efficiency, the dosage is reduced on a large scale, the using amount of the bird-repelling pheromone is saved, the cost is saved, and the aim of repelling is fulfilled. The humate contains-COOH and-NH2Active functional groups such as-OH, -CO and some N, O heteroatoms, etc., are active natural macromolecules which widely exist in the nature, have good adsorption and complexation performance, can provide various nutrient components for plants, and endow the gel with natural biological activity; and the humic acid raw material is easy to obtain, simple to operate and green and environment-friendly. The humic acid type bird repelling pheromone core-shell structure gel prepared by the invention can efficiently repel birds, prevent insects, prevent corrosion and inhibit the growth of mold on one hand, and can provide multiple effects of multiple trace elements, nutrient components, sustained-release drugs and the like for plants on the other hand. The product of the invention has low cost, can be accepted by most fruit growers, reduces the use of chemical pesticides, can effectively drive birds without injuring the birds, and is environment-friendly.
The reaction principle of the method is shown in figure 1, the humic acid type bird repelling pheromone core-shell structure gel prepared by the method can uninterruptedly release bird repelling and insect repelling for a long time, and the added natural substance humic acid and some antiseptic and emulsifying substances thereof can effectively inhibit the growth of mould for plants.
Drawings
FIG. 1 is a reaction mechanism of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following will clearly and completely describe the technical solution of the present invention with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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. The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
It is noted that the terms first, second and the like in the description and in the claims of the present invention are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The preparation method of the humic acid type bird repelling pheromone core-shell structure gel comprises the following steps:
1) weighing weathered coal, lignite or peat coal samples which are dried by 80 meshes, adding diluted hydrochloric acid according to the solid-liquid ratio of 1g (9-13) mL, heating, boiling and activating, cooling, washing precipitates to be neutral, adding a sodium hydroxide solution with the concentration of 10-20% according to the solid-liquid ratio of 1 (8-12), heating and stirring in a boiling water bath at 100 ℃ for 1-3 hours, cooling to room temperature, carrying out centrifugal filtration, and weighing the mass of filter residues; and (3) adding dilute hydrochloric acid into the filtrate to adjust the pH value to 1-3, standing for 24 hours, filtering, collecting precipitates, and drying to constant weight to obtain humic acid.
2) Mixing the span and the Tween solution in the mass ratio of 1 (1-3), and adding 50-100 mL of liquid paraffin for fully mixing to obtain an oil phase solution for later use.
3) Dissolving 1-1.5 g of humic acid in a strong base solution with the pH value of 11-14 to obtain a humate solution, weighing 0.9-1 g of a cellulose solution, mixing the two solutions, adding 6-8 g of acrylic acid, adjusting the pH value to 8-9, adding 0.04-0.08 g of potassium persulfate KPS, 0.01-0.02 g N, N-Methylene Bisacrylamide (MBA) and 0.1-0.4 g of bird repelling pheromone, heating to 70 ℃ to perform a crosslinking reaction for 1-2 hours, adding the oil phase solution in the step 2) under a high-speed stirring condition to perform emulsification, reducing the stirring speed, adding 0.3-0.6 g of NaHSO3And (3) carrying out reaction to obtain the water-in-oil type core-shell structure bird repelling gel.
4) Removing the upper oil phase, washing the lower oil phase with ethyl acetate, absolute ethyl alcohol and distilled water, and drying to obtain the water-in-oil type core-shell structure bird-repelling gel.
The present invention is further described in detail below with reference to specific examples:
example 1
A humic acid type bird repellent pheromone core-shell structure gel comprises the following raw material components in parts by weight:
humic acid (weathered coal), ethyl cellulose, acrylic acid, bird repellent pheromone (methyl anthranilate), emulsifier (span 20, tween 80 and liquid paraffin), initiator and cross-linking agent. The adding ratio in parts by mass is 10:9:6:1:2:0.4: 0.1.
The preparation process of the humic acid type green environment-friendly antibacterial insect-prevention pheromone polymeric membrane comprises the following steps:
1) weighing a weathered coal sample which is dried by 80 meshes according to the solid-to-liquid ratio of 1:9 (g.mL)-1) Adding dilute hydrochloric acid according to the proportion, heating, boiling, activating, cooling, washing the precipitate to be neutral, adding 10% sodium hydroxide solution according to the solid-to-liquid ratio of 1:8, heating and stirring in a boiling water bath at 100 ℃ for 1 hour, cooling to room temperature, carrying out centrifugal filtration, and weighing the mass of the filter residue; and adding dilute hydrochloric acid into the filtrate to adjust the pH value to 1, standing for 24h, filtering, collecting precipitate, and drying to constant weight to obtain the humic acid.
2) Mixing the span 20 and the Tween 80 solution in a mass ratio of 1:1, and adding 50mL of liquid paraffin for fully mixing to obtain an oil phase solution for later use.
3) Dissolving 1.0g of humic acid in potassium hydroxide with the pH value of 13 to obtain a potassium humate solution, weighing 0.9g of ethyl cellulose solution, mixing the two solutions, adding 6mL of acrylic acid, adjusting the pH value to 8, adding 0.04g of KPS, 0.01g of MBA and 0.1g of methyl anthranilate, heating to 70 ℃ for crosslinking reaction for 2 hours, adding the oil phase solution in the step 2) under the condition of high-speed stirring for emulsification, reducing the stirring speed, adding 0.4g of NaHSO3And (3) carrying out reaction to obtain the water-in-oil type core-shell structure bird repelling gel.
4) Removing the upper oil phase of the crude product, repeatedly washing the lower layer with ethyl acetate, absolute ethyl alcohol and distilled water respectively, and drying to obtain humic acid type bird-repelling pheromone core-shell structure gel.
Example 2
A humic acid type bird repellent pheromone core-shell structure gel comprises the following raw material components in parts by weight:
humic acid (lignite), ethyl cellulose, acrylic acid, bird repellent pheromone (methyl anthranilate), emulsifier (span 40, tween 80 and liquid paraffin), initiator and cross-linking agent. The adding proportion of the components is 14:10:8:4:6:0.4:0.1 in parts by mass
The preparation process of the humic acid type green environment-friendly antibacterial insect-prevention pheromone polymeric membrane comprises the following steps:
1) weighing 80 mesh dried lignite sample according to solid-liquid ratio of 1: 13 (g.mL)-1) Adding dilute hydrochloric acid according to the proportion, heating, boiling, activating, cooling, washing the precipitate to be neutral, adding 20% of sodium hydroxide solution according to the solid-to-liquid ratio of 1:12, heating and stirring in a boiling water bath at 100 ℃ for 1 hour, cooling to room temperature, carrying out centrifugal filtration, and weighing the mass of the filter residue; and (3) adding dilute hydrochloric acid into the filtrate to adjust the pH value to 1, standing for 24 hours, filtering, collecting precipitates, and drying to constant weight to obtain humic acid.
2) Mixing the span 40 and the Tween 80 solution in a mass ratio of 1:5, and adding 70mL of liquid paraffin for fully mixing to obtain an oil phase solution for later use.
3) Dissolving 1.4g of humic acid in potassium hydroxide with the pH value of 12 to obtain a humate solution, weighing 1g of ethyl cellulose solution, mixing the two, adding 8mL of acrylic acid, adjusting the pH value to 8, adding 0.04g of KPS, 0.01g of MBA and 0.4g of methyl anthranilate, heating to 70 ℃ for crosslinking reaction for 2 hours, adding the oil phase solution in the step 2) under the condition of high-speed stirring for emulsification, reducing the stirring speed, adding 0.5g of NaHSO3And (3) carrying out reaction to obtain the water-in-oil type core-shell structure bird repelling gel.
4) Removing the upper oil phase of the crude product, repeatedly washing the lower layer with ethyl acetate, absolute ethyl alcohol and distilled water respectively, and drying to obtain humic acid type bird-repelling pheromone core-shell structure gel.
Example 3
A humic acid type bird repellent pheromone core-shell structure gel comprises the following raw material components in parts by weight:
humic acid (peat), hydroxypropyl methylcellulose, acrylonitrile, bird repellent pheromone (methyl anthranilate), emulsifier (span 60, tween 80 and liquid paraffin), initiator and cross-linking agent. The adding ratio of the components in parts by mass is 15:10:8:4:6:0.8:0.2
The preparation process of the humic acid type green environment-friendly antibacterial insect-prevention pheromone polymeric membrane comprises the following steps:
1) weighing peat sample dried by 80 meshes according to the solid-to-liquid ratio of 1:10 (g.mL)-1) Adding dilute sulfuric acid according to the proportion, heating, boiling, activating, cooling, washing the precipitate to be neutral, adding 20% of sodium hydroxide solution according to the solid-to-liquid ratio of 1:10, heating and stirring in a boiling water bath at 100 ℃ for a certain time, cooling to room temperature, carrying out centrifugal filtration, and weighing the mass of the filter residue; and adding dilute hydrochloric acid into the filtrate to adjust the pH to 2, standing for 24h, filtering, collecting precipitate, and drying to constant weight to obtain humic acid.
2) Mixing the span 20 and the Tween 80 solution in a mass ratio of 1:4, and adding 50mL of liquid paraffin for fully mixing to obtain an oil phase solution for later use.
3) Dissolving 1.5g of humic acid in potassium hydroxide with the pH value of 14 to obtain a potassium humate solution, weighing 1g of hydroxypropyl methyl cellulose solution, mixing the two solutions, adding 8mL of acrylic acid, adjusting the pH value to 8, adding 0.08g of KPS, 0.02g of MBA and 0.4g of methyl anthranilate, heating to 70 ℃ for crosslinking reaction for 2 hours, adding the oil phase solution in the step 2) under the condition of high-speed stirring for emulsification, reducing the stirring speed, adding 0.5g of NaHSO3And (3) carrying out reaction to obtain the water-in-oil type core-shell structure bird repelling gel.
4) Removing the upper oil phase of the crude product, repeatedly washing the lower layer with ethyl acetate, absolute ethyl alcohol and distilled water, and drying to obtain the humic acid type bird repellent pheromone core-shell structure gel.
Example 4
A humic acid type bird repellent pheromone core-shell structure gel comprises the following raw material components in parts by weight: humic acid (lignite), carboxymethyl cellulose, acrylonitrile, bird repellent pheromone (methyl anthranilate, cinnamaldehyde and camphor in a mass ratio of 2:1:1), emulsifier (span, tween and liquid paraffin), initiator and cross-linking agent. The adding ratio in parts by mass is 12:8:8:4:5:0.4: 0.15.
The preparation process of the humic acid type green environment-friendly antibacterial insect-prevention pheromone polymeric membrane comprises the following steps:
1) weighing the dried lignite sample which passes through an 80-mesh sieve according to the solid-to-liquid ratio of 1:10 (g.mL)-1) Adding dilute hydrochloric acid according to the proportion, heating, boiling, activating, cooling, washing the precipitate to be neutral, adding 15% sodium hydroxide solution according to a certain solid-to-liquid ratio of 1:8, heating and stirring in a boiling water bath at 100 ℃ for a certain time, cooling to room temperature, carrying out centrifugal filtration, and weighing the mass of the filter residue; and adding dilute hydrochloric acid into the filtrate to adjust the pH value to 3, standing for 24h, filtering, collecting precipitates, and drying to constant weight to obtain the humic acid.
2) Mixing the span 20 and the Tween 80 solution in a mass ratio of 1:3, and adding 80mL of liquid paraffin for fully mixing to obtain an oil phase solution for later use.
3) Dissolving 1.2g of humic acid in potassium hydroxide with the pH value of 11 to obtain a potassium humate solution, weighing 0.8g of carboxymethyl cellulose solution, mixing the two solutions, adding 8mL of acrylic acid, adjusting the pH value to 8, adding 0.04g of KPS, 0.015g of MBA,0.4g of methyl anthranilate, cinnamaldehyde and camphor, heating to 70 ℃ for carrying out crosslinking reaction for 2 hours, adding the oil phase solution in the step 2) under the condition of high-speed stirring for emulsification, reducing the stirring speed, adding 0.5g of NaHSO3And (3) carrying out reaction to obtain the water-in-oil type core-shell structure bird repelling gel.
4) Removing the upper oil phase of the crude product, repeatedly washing the lower layer with ethyl acetate, absolute ethyl alcohol and distilled water respectively, and drying to obtain humic acid type bird-repelling pheromone core-shell structure gel.
Example 5
A humic acid type bird repellent pheromone core-shell structure gel comprises the following raw material components in parts by weight: humic acid (lignite), carboxymethyl cellulose, acrylonitrile, bird repellent pheromone (methyl anthranilate, camphor and menthol are 6:1:1 in mass ratio), emulsifier (span, tween and liquid paraffin), initiator and cross-linking agent. The adding ratio of the components in parts by mass is 12:8:8:4:5:0.4: 0.2. The preparation process of the humic acid type green environment-friendly antibacterial insect-prevention pheromone polymeric membrane comprises the following steps:
1) weighing 80 mesh dried lignite sample according to solid-liquid ratio of 1:10 (g.mL)-1) Adding dilute hydrochloric acid according to the proportion, heating, boiling, activating, cooling and washing precipitateAdding 10% sodium hydroxide solution according to the solid-to-liquid ratio of 1:8 until the mixture is neutral, heating and stirring the mixture in a boiling water bath at the temperature of 100 ℃ for 1 hour, cooling the mixture to room temperature, carrying out centrifugal filtration, and weighing the mass of the filter residue; and adding dilute hydrochloric acid into the filtrate to adjust the pH to 2, standing for 24h, filtering, collecting precipitate, and drying to constant weight to obtain humic acid.
2) Mixing the span 20 and the Tween 80 solution in a mass ratio of 1:3, and adding 60mL of liquid paraffin for fully mixing to obtain an oil phase solution for later use.
3) Dissolving 1.2g of humic acid in potassium hydroxide with the pH value of 13 to obtain a potassium humate solution, weighing 0.8g of carboxymethyl cellulose solution, mixing the two solutions, adding 8mL of acrylic acid, adjusting the pH value to 8, adding 0.04g of KPS, 0.02g of MBA and 0.4g of bird repelling pheromone, heating to 70 ℃ for crosslinking reaction for 2 hours, adding the oil phase solution in the step 2) under the condition of high-speed stirring for emulsification, reducing the stirring speed, adding 0.4g of NaHSO3And (3) carrying out reaction to obtain the water-in-oil type core-shell structure bird repelling gel.
4) Removing the upper oil phase of the crude product, repeatedly washing the lower layer with ethyl acetate, absolute ethyl alcohol and distilled water respectively, and drying to obtain humic acid type bird-repelling pheromone core-shell structure gel.
Example 6
A humic acid type bird repellent pheromone core-shell structure gel comprises the following raw material components in parts by weight: humic acid (lignite), carboxymethyl cellulose, acrylonitrile, bird repellent pheromone (methyl anthranilate, cinnamide and menthol in a mass ratio of 1:1:1), emulsifier (span, tween and liquid paraffin), initiator and cross-linking agent. The adding ratio in parts by mass is 12:8:8:4:5:0.4: 0.15.
The preparation process of the humic acid type green environment-friendly antibacterial insect-prevention pheromone polymeric membrane comprises the following steps:
1) weighing 80 mesh dried lignite sample according to solid-liquid ratio of 1:10 (g.mL)-1) Adding dilute hydrochloric acid according to the proportion, heating, boiling and activating, cooling, washing the precipitate to be neutral, adding sodium hydroxide solutions with different concentrations according to a certain solid-to-liquid ratio, heating and stirring in a boiling water bath at 100 ℃ for a certain time, cooling to room temperature, centrifugally filtering, weighing the mass of the filter residue(ii) a And adding dilute hydrochloric acid into the filtrate to adjust the pH to 2, standing for 24h, filtering, collecting precipitate, and drying to constant weight to obtain humic acid.
2) Mixing the span 20 and the Tween 80 solution in a mass ratio of 1:4, and adding 80mL of liquid paraffin for fully mixing to obtain an oil phase solution for later use.
3) Dissolving 1.2g of humic acid in potassium hydroxide with the pH value of 14 to obtain a potassium humate solution, weighing 0.8g of carboxymethyl cellulose solution, mixing the two solutions, adding 8mL of acrylic acid, adjusting the pH value to 8, adding 0.04g of KPS, 0.015g of MBA,0.4g of methyl anthranilate, cinnamide and menthol, heating to 70 ℃ for crosslinking reaction for 2 hours, adding the oil phase solution in the step 2) under the condition of high-speed stirring for emulsification, reducing the stirring speed, adding 0.4g of NaHSO3And (3) carrying out reaction to obtain the water-in-oil type core-shell structure bird repelling gel.
4) Removing the upper oil phase of the crude product, repeatedly washing the lower layer with ethyl acetate, absolute ethyl alcohol and distilled water respectively, and drying to obtain humic acid type bird-repelling pheromone core-shell structure gel.
Example 7
A humic acid type bird repellent pheromone core-shell structure gel comprises the following raw material components in parts by weight:
humic acid (peat), carboxymethyl cellulose, acrylonitrile, bird repellent pheromone (methyl anthranilate and camphor in a mass ratio of 4:3:1), emulsifier (span, tween and liquid paraffin), initiator and cross-linking agent. The adding ratio of the components in parts by mass is 12:8:8:4:5:0.4: 0.2.
The preparation process of the humic acid type green environment-friendly antibacterial insect-prevention pheromone polymeric membrane comprises the following steps:
1) weighing peat sample dried by 80 meshes according to the solid-to-liquid ratio of 1:10 (g.mL)-1) Adding dilute hydrochloric acid according to the proportion, heating, boiling, activating, cooling, washing the precipitate to be neutral, adding 10% sodium hydroxide solution according to the solid-to-liquid ratio of 1:10, heating and stirring in a boiling water bath at 100 ℃ for a certain time, cooling to room temperature, carrying out centrifugal filtration, and weighing the mass of the filter residue; and adding dilute hydrochloric acid into the filtrate to adjust the pH value to 1.5, standing for 24h, filtering, collecting precipitate, and drying to constant weight to obtain the humic acid.
2) And mixing the span 20 and the Tween 80 solution in a mass ratio of 1:3, and adding 80mL of liquid paraffin for fully mixing for later use.
3) Dissolving 1.2g of humic acid in potassium hydroxide with the pH value of 12 to obtain a potassium humate solution, weighing 0.8g of carboxymethyl cellulose solution, mixing the two solutions, adding 8mL of acrylic acid, adjusting the pH value to 8, adding 0.04g of KPS, 0.02g of MBA and 0.4g of bird repelling pheromone, heating to 70 ℃ for crosslinking reaction for 2 hours, adding the oil phase solution in the step 2) under the condition of high-speed stirring for emulsification, reducing the stirring speed, adding 0.5g of NaHSO3And (3) carrying out reaction to obtain the water-in-oil type core-shell structure bird repelling gel.
4) Removing the upper oil phase of the crude product, repeatedly washing the lower layer with ethyl acetate, absolute ethyl alcohol and distilled water respectively, and drying to obtain humic acid type bird-repelling pheromone core-shell structure gel.
The following tests were carried out on the humic acid type bird repelling pheromone core-shell structure gel and the commercially available bird repelling agent prepared in examples 1 to 7, and the results are as follows:
(1) testing of bird repelling rate of humic acid type bird repelling pheromone core-shell structure gel
Blank cases and bird flying defects are used as a contrast, a sampling investigation method is adopted to determine the expelling effect in different cases of bird implementation in gardens for investigation, a high-sensitivity wall-mounted sound sensor is used for monitoring the sound emitted by the birds, the sound is simulated and converted into the number of the birds through the modern technology, and the results are shown in table 1
Table 1 results of different examples on garden treatment
Figure BDA0003090760810000131
As can be seen from table 1, compared with the blank examples, the examples 1 to 7 and the common bird repellent have a significant effect on expelling birds, the increase of the examples 1 to 7 is more significant, the bird repelling effect in the examples 1 to 7 is more significant, the data of the examples 1 to 7 and the common bird repellent tend to increase before 21 days, the common bird repellent is largely decomposed after 21 days, so that the bird repelling rate is reduced, and the humic acid type bird repelling pheromone core-shell structure gel basically remains unchanged.
(2) Decomposition rate test of humic acid type bird repelling pheromone core-shell structure gel
The method for testing the decomposition rate comprises the following steps:
weighing prepared and dried humic acid type bird-repelling pheromone core-shell structure gel m1g, completely burying in natural soil with water retention capacity and relative humidity of 60%, culturing, adding sulfuric acid solution with pH of 3.0 to keep pH of soil constant, taking out gel after 30 days, cleaning, oven drying, and weighing sample mass m2The decomposition rate was calculated as follows:
the results are shown in table 2 below:
Figure BDA0003090760810000141
TABLE 2 decomposition rate results for different examples and common bird repellents
Figure BDA0003090760810000142
As can be seen from table 2, in examples 1 to 7, compared with a common bird repellent product, the decomposition is greatly different, the change range of the decomposition rate in the examples is small, and by preparing a core-shell structure, humic acid and bird repellent pheromone are combined through chemical bonds, which indicates that the product is slow in decomposition speed, and the product can exert the bird repellent effect stably for a long time.

Claims (8)

1. A humic acid type bird repellent pheromone core-shell structure gel is characterized by comprising the following raw materials in parts by mass: 10-15 parts of humate, 9-10 parts of cellulose, 6-8 parts of hydrophilic monomer, 1-4 parts of bird repelling pheromone, 2-6 parts of emulsifier, 0.4-0.8 part of initiator and 0.1-0.2 part of cross-linking agent;
the hydrophilic monomer is one of acrylic acid, acrylamide and acrylonitrile;
the bird-repelling pheromone substance is one or more of methyl anthranilate, cinnamamide, cinnamaldehyde, menthol and camphor;
the preparation method of the humic acid type bird repelling pheromone core-shell structure gel comprises the following steps: dissolving humate and cellulose in water, adding a hydrophilic monomer, a bird repelling pheromone, an initiator and a cross-linking agent, carrying out a cross-linking reaction, and adding an emulsifier under stirring to carry out an emulsion reaction to obtain the water-in-oil type core-shell structure bird repelling gel.
2. The humic acid type bird repellent pheromone core-shell structure gel of claim 1, wherein the humic acid salt is prepared from weathered coal, lignite or peat.
3. The humic acid type bird repellent pheromone core-shell structure gel according to claim 1, wherein the cellulose is one of carboxymethyl cellulose, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose, ethyl cellulose and hydroxyethyl cellulose.
4. The humic acid type bird repellent pheromone core-shell structure gel of claim 1, wherein the emulsifier is span 20, span 40, span 60, tween 20, tween 60, tween 80, liquid paraffin and NaHSO3One or more of them.
5. The humic acid type bird repellent pheromone core-shell structure gel of claim 1, wherein the initiator is persulfate.
6. The humic acid type bird repellent pheromone core-shell structure gel of claim 1, wherein the cross-linking agent is N, N-methylene bisacrylamide.
7. The preparation method of the humic acid type bird repelling pheromone core-shell structure gel according to any one of claims 1 to 6 is characterized in that humic acid salt and cellulose are dissolved in water, hydrophilic monomers, bird repelling pheromones, initiators and cross-linking agents are added for cross-linking reaction, and emulsifying agents are added under stirring conditions for emulsification reaction to obtain the water-in-oil type bird repelling gel with the core-shell structure.
8. The preparation method of the humic acid type bird repelling pheromone core-shell structure gel according to claim 7 is characterized by comprising the following steps:
1) dissolving humic acid in a strong base solution with the pH value of 11-14 to obtain a humate solution, and mixing the humate solution with a cellulose aqueous solution to obtain a mixed solution 1;
2) adding a hydrophilic monomer into the mixed solution 1, and adjusting the pH value to 8-9 to obtain a mixed solution 2;
3) adding the bird-repelling pheromone, the initiator and the cross-linking agent into the mixed solution 2, heating to 60-70 ℃, and carrying out cross-linking reaction for 1-2 hours to obtain a reaction solution 1;
4) adding an emulsifier into the reaction solution 1 under the condition of high-speed stirring for emulsification, and reacting to obtain the water-in-oil type core-shell structure bird-repelling gel;
5) and (3) respectively washing the water-in-oil type bird repelling gel with the core-shell structure with ethyl acetate, absolute ethyl alcohol and distilled water for 3-5 times, and drying to obtain the humic acid type bird repelling pheromone core-shell structure gel.
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