CN113121965A - Insect pheromone-containing biodegradable agricultural film and preparation method thereof - Google Patents

Insect pheromone-containing biodegradable agricultural film and preparation method thereof Download PDF

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CN113121965A
CN113121965A CN202110437277.0A CN202110437277A CN113121965A CN 113121965 A CN113121965 A CN 113121965A CN 202110437277 A CN202110437277 A CN 202110437277A CN 113121965 A CN113121965 A CN 113121965A
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insect pheromone
agricultural film
film containing
biodegradable agricultural
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宋洁
韩家旋
李龙
陈莉君
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16Dicarboxylic acids and dihydroxy compounds
    • C08G63/20Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/07Aldehydes; Ketones
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/10Esters; Ether-esters
    • C08K5/101Esters; Ether-esters of monocarboxylic acids

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Abstract

The invention discloses a biodegradable agricultural film containing insect pheromone and a preparation method thereof, belonging to the field of agricultural application. The biodegradable agricultural film containing the insect pheromone is prepared by melting and blending the hydrophilic modified PBS and the insect pheromone to prepare composite master batches and carrying out a film blowing process on the obtained composite master batches. The preparation method is simple, low in energy consumption, time-saving and convenient to machine and form. The prepared biodegradable agricultural film containing the insect pheromone is based on the biodegradable material hydrophilic modified PBS, and is added with the insect pheromone for preventing and controlling prodenia litura, beet armyworm and diamond back moth, thereby achieving the effect of preventing and controlling insect pests. The biodegradable agricultural film containing the insect pheromone solves the problems of environmental pollution caused by traditional agriculture and increasingly poor control effect of chemical pesticides, and meanwhile, the biodegradable agricultural film is degraded in use and fully absorbed by soil, so that higher added value is given to the agricultural film, and the effect of controlling insect pests is achieved.

Description

Insect pheromone-containing biodegradable agricultural film and preparation method thereof
Technical Field
The invention belongs to the field of agricultural application, and relates to a biodegradable agricultural film containing insect pheromone and a preparation method thereof.
Background
With the continuous improvement of modern people's living standard, people have higher and higher requirements on the variety and quality of vegetables, and the agricultural greenhouse is an agricultural facility for improving the yield of crops, improving the quality and implementing out-of-season planting to improve the agricultural production efficiency and benefit, and is widely applied to the field of vegetable planting. In the planting process of different seasons, prodenia litura, beet armyworm and diamond back moth are three major pests of vegetables, have high reproduction rate, wide host range and strong diffusion capacity, and greatly influence the quality and yield of the vegetables.
At present, chemical pesticides are adopted to prevent and treat vegetables, the prevention and treatment effects are increasingly poor along with the application process of the pesticides, and the quality of the vegetables is reduced due to the influence of chemical components. Meanwhile, chemical pesticides can cause certain toxic pollution and influence the ecological environment. Due to the increasing requirements for vegetable quality and environmental protection, the research of using insect pheromones to prevent and control insect pests is increasingly gaining attention. According to the physiological and biochemical characteristics and the behavioral characteristics of insects, the insect pheromone can cause the male insects to be 'disoriented' and interfere mating to achieve the effect of preventing and controlling insect pests.
Most of the insect pheromone products in the current market place a device with the insect pheromone at a fixed point to achieve the effect of preventing and controlling insect pests, but the application mode has a plurality of defects and can not be applied in a large scale, for example, the application mode of the fixed point placement can not achieve full coverage and the concentration of the insect pheromone in the space is not uniform, but the part with lower concentration is seriously damaged; the using mode is greatly influenced by weather and rain, and the releasing process is lack of long-term effectiveness.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a biodegradable agricultural film containing insect pheromone and a preparation method thereof, which solve the problems of uneven distribution and short long-acting property of the insect pheromone in the using process of the existing product and achieve the effects of uniform release and long-acting prevention and control.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a biodegradable agricultural film containing insect pheromone, which comprises the steps of carrying out melt blending on hydrophilic modified PBS and the insect pheromone to prepare composite master batches, and carrying out film blowing on the obtained composite master batches to prepare the biodegradable agricultural film containing the insect pheromone.
Preferably, the insect pheromones include: at least one of (Z) -11-hexadecenal, (Z) -11-hexadecen-1-ol acetic acid, (Z) -11-hexadecenol, (Z, E) -9, 12-tetradecadiene-1-ol acetate, and (Z) -9-tetradecenol.
More preferably, (Z) -11-hexadecenal, (Z) -11-hexadecen-1-ol acetic acid, (Z) -11-hexadecenol, (Z, E) -9, 12-tetradecadiene-1-ol acetate, and (Z) -9-tetradecenol are compounded in a mass ratio of 0-1: 0-1.2: 0-0.8: 0-1: 0-0.5, wherein at least one of the mass ratios is not zero.
Preferably, the mixing mass ratio of the hydrophilic modified PBS to the insect pheromone is 1: 0.2-0.3.
Preferably, the temperature of the melt blending is 110-120 ℃, and the temperature of the film blowing process is 130-150 ℃.
Preferably, the hydrophilically modified PBS is prepared by the following steps: uniformly mixing butanediol, succinic acid and a third monomer, performing dehydration condensation reaction to obtain a reaction mixture, adding butyl titanate into the obtained reaction mixture to perform polymerization reaction to obtain a viscous product mixture, cooling the obtained viscous product mixture, and removing impurities to obtain hydrophilic modified PBS; wherein, the third monomer is polyhydroxy hydrophilic monomer.
Further preferably, the hydrophilic polyhydroxy monomer is glycerol, trihydroxymethylpropane, trimethylolethane, anhydrous phloroglucinol, phloroglucinol dihydrate, 1,2, 4-benzenetriol, 2, 3, 4-trihydroxybenzaldehyde, 1,4, 5-trihydroxy-2-pentanone or 1,3, 5-trihydroxy-2-bromobenzene.
More preferably, the molar ratio of the butanediol to the succinic acid to the third monomer is 1:1: 0.15-0.30; the butyl titanate is 0.3-0.8% of the butanediol.
Further preferably, the temperature of the dehydration condensation reaction is 160-170 ℃ and the time is 3-3.5 h.
Further preferably, the temperature of the polymerization reaction is 210 to 220 ℃.
The invention also discloses a biodegradable agricultural film containing the insect pheromone, which is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a biodegradable agricultural film containing insect pheromone, which adopts a biodegradable material PBS as a matrix and selects a hydrophilic modified PBS, so that the hydrophilicity and the water retention of the agricultural film are improved, and the growth environment of greenhouse vegetables is improved. Insect pheromone is added, and the effect is released to the air through the degradation characteristic of the insect pheromone, so that the male insects are attracted, and the female insects cannot be positioned for mating, so that the effect of preventing and treating insect pests is achieved by interfering mating, and the effect of preventing and treating prodenia litura, beet armyworm and plutella xylostella is achieved. The preparation method disclosed by the invention is simple, low in energy consumption, time-saving and convenient to machine and form, and lays a foundation for the use of various agricultural films.
Further, by selecting a reasonable insect pheromone substance, targeted control can be performed on different types of pests. Meanwhile, the defects of poor control effect and environmental pollution of the traditional pesticide are overcome, and the effect of controlling insect pests is achieved.
Furthermore, the third type of hydrophilic monomer of polyhydroxy is selected to modify PBS, so that the hydrophilicity and the water retention of the agricultural film are improved, the growth environment of greenhouse vegetables is improved, the compatibility of PBS is increased, and the PBS can be better blended with insect pheromone. By synthesizing degradable PBS as a coating material and releasing the insect pheromone through the slow degradation of the PBS, the problems of uneven distribution and short long-acting property of the insect pheromone in the existing use process are solved, and the problem of recycling the discarded agricultural film is solved.
The invention discloses a biodegradable agricultural film containing insect pheromone, which is prepared by the preparation method, wherein the biodegradable agricultural film containing the insect pheromone is used for replacing the traditional chemical insecticide, and the insect pheromone is slowly released by the slow degradation of the agricultural film, so that the long-acting control effect is achieved. Meanwhile, the problem of environmental pollution caused by chemical pesticides is reduced, and higher-quality vegetables can be obtained. The biodegradable agricultural film is degraded in use and fully absorbed by soil, so that higher added value is given to the agricultural film, and the agricultural film conforms to the sustainable development of agriculture and the development direction of green agriculture.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiments of the present invention will be clearly and completely described below 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.
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.
A method for preparing biodegradable agricultural film containing insect pheromone comprises the following raw materials: butanediol, succinic acid, a third monomer, insect pheromone and butyl titanate.
The third monomer is polyhydroxy hydrophilic monomer, such as glycerol, trihydroxy methyl propane, trimethylolethane, anhydrous phloroglucinol, phloroglucinol dihydrate, 1,2, 4-benzenetriol, 2, 3, 4-trihydroxy benzaldehyde, 1,4, 5-trihydroxy-2-pentanone, 1,3, 5-trihydroxy-2-bromobenzene, etc.
The insect pheromones are: (Z) -11-hexadecene aldehyde, (Z) -11-hexadecene-1-ol acetic acid, (Z) -11-hexadecene alcohol, (Z, E) -9, 12-tetradecadiene-1-ol acetic ester, and (Z) -9-tetradecene alcohol are compounded according to the mass ratio of (1: 1-1.2: 0.5-0.8: 1: 0.3-0.5).
The preparation method for preparing the biodegradable agricultural film containing the insect pheromone by adopting the preparation raw materials of butanediol, succinic acid, the third monomer, the insect pheromone and butyl titanate comprises the following steps:
(1) taking raw materials: butanediol, succinic acid, a third monomer and butyl titanate. Wherein the molar ratio of the butanediol to the succinic acid to the third monomer is as follows: 1:1 (0.15-0.30); butyl titanate accounts for 0.3 to 0.8 percent of the amount of the polymer monomer substance.
(2) Adding butanediol, succinic acid and a third monomer into a dry three-neck flask with a stirrer, introducing nitrogen and an elbow connecting pipe, stirring and heating to about 160-170 ℃, and starting a dehydration condensation reaction for 3-3.5 hours to obtain a reaction mixture. And then removing nitrogen, adding butyl titanate into the obtained reaction mixture, sealing, heating to about 210-220 ℃, starting polymerization reaction, and stopping stirring until the system in the three-neck flask is viscous and the micromolecule product (water) reaches a theoretical value to obtain a viscous product mixture. Taking out the prepared viscous product mixture material, cooling, dissolving with chloroform, pouring into alcohol, and precipitating to obtain hydrophilic modified PBS (poly butylene succinate).
(3) Melting and blending hydrophilic modified PBS and insect pheromone at the temperature of 110-120 ℃ according to the mass ratio of (1: 0.2-0.3) to prepare composite master batches, and then carrying out a film blowing process on the obtained composite master batches, wherein the temperature of the film blowing process is controlled at 130-150 ℃ to prepare the biodegradable agricultural film containing the insect pheromone.
In the preparation method of the biodegradable agricultural film containing the insect pheromone, the hydrophilic modified PBS is a biodegradable material, and a third monomer is added in the synthesis process of the hydrophilic modified PBS to increase the water retention property of the hydrophilic modified PBS; and the insect pheromone is blown after blending the insect pheromone and the hydrophilic modified PBS through melt blending, thereby meeting the requirement that the finally prepared agricultural film contains the insect pheromone.
The invention is further illustrated by the following specific examples:
the first embodiment is as follows:
a method for preparing a biodegradable agricultural film containing insect pheromone comprises the following raw material components: the molar ratio of butanediol, succinic acid and the third monomer is 1:1: 0.19; the amount of butyl titanate added as catalyst was 0.5% of the amount of butanediol or succinic acid material. The third monomer is trimethylolethane, and the insect pheromone is: (Z) -11-hexadecene aldehyde, (Z) -11-hexadecene-1-ol acetic acid, (Z) -11-hexadecene alcohol, (Z, E) -9, 12-tetradecadiene-1-ol acetate, and (Z) -9-tetradecene alcohol are compounded according to the mass ratio of (1: 1: 0.8: 1: 0.5).
The preparation process comprises the following steps:
(1) adding butanediol, succinic acid and a third monomer into a dry three-neck flask with a stirrer, introducing nitrogen and an elbow connecting pipe, stirring and heating to about 170 ℃, and starting a dehydration condensation reaction for 3 hours. Then removing nitrogen, adding tetrabutyl titanate, sealing, heating to about 210 ℃, starting polymerization reaction, and stopping stirring until the system in the three-neck flask is viscous and the micromolecule product (water) reaches a theoretical value to obtain a viscous product mixture. The prepared viscous product mixture material is taken out to be cooled, dissolved by chloroform and poured into alcohol to be separated out, and the hydrophilic modified PBS is prepared.
(2) Melting and blending the hydrophilic modified PBS and the insect pheromone at the temperature of 110 ℃ according to the mass ratio (1: 0.30) to prepare composite master batches, and then blowing the composite master batches into a film, wherein the film blowing temperature is controlled at 130 ℃ to prepare the biodegradable agricultural film containing the insect pheromone.
Example two:
a method for preparing a biodegradable agricultural film containing insect pheromone comprises the following raw material components: taking butanediol, succinic acid and a third monomer in a molar ratio of 1:1: 0.19; the amount of butyl titanate added as catalyst was 0.5% of the amount of butanediol or succinic acid material. The third monomer is trimethylolethane, and the insect pheromone is: (Z) -11-hexadecene aldehyde, (Z) -11-hexadecene-1-ol acetic acid, (Z) -11-hexadecene alcohol, (Z, E) -9, 12-tetradecadiene-1-ol acetate, and (Z) -9-tetradecene alcohol are compounded according to the mass ratio of (1: 1: 0.6: 1: 0.4).
The preparation process comprises the following steps:
(1) adding butanediol, succinic acid and a third monomer into a dry three-neck flask with a stirrer, introducing nitrogen and an elbow connecting pipe, stirring and heating to about 170 ℃, and starting a dehydration condensation reaction for 3 hours. Then removing nitrogen, adding tetrabutyl titanate, sealing, heating to about 210 ℃, starting polymerization reaction, and stopping stirring until the system in the three-neck flask is viscous and the micromolecule product (water) reaches a theoretical value to obtain a viscous product mixture. The prepared viscous product mixture material is taken out to be cooled, dissolved by chloroform and poured into alcohol to be separated out, and the hydrophilic modified PBS is prepared.
(2) Melting and blending the hydrophilic modified PBS and the insect pheromone at the temperature of 110 ℃ according to the mass ratio of (1: 0.25) to prepare composite master batches, and then blowing the composite master batches into a film, wherein the film blowing temperature is controlled at 130 ℃ to prepare the biodegradable agricultural film containing the insect pheromone.
Example three:
a method for preparing a biodegradable agricultural film containing insect pheromone comprises the following raw material components: taking butanediol, succinic acid and a third monomer in a ratio of 1:1: 0.19; the amount of butyl titanate added as catalyst was 0.5% of the amount of butanediol or succinic acid material. The third monomer is 1,2, 4-benzenetriol, and the insect pheromone is as follows: (Z) -11-hexadecene aldehyde, (Z) -11-hexadecene-1-ol acetic acid, (Z) -11-hexadecene alcohol, (Z, E) -9, 12-tetradecadiene-1-ol acetate, and (Z) -9-tetradecene alcohol are compounded according to the mass ratio of (1: 1.1: 0.5: 1: 0.3).
The preparation process comprises the following steps:
(1) adding butanediol, succinic acid and a third monomer into a dry three-neck flask with a stirrer, introducing nitrogen and an elbow connecting pipe, stirring and heating to about 160 ℃, and starting a dehydration condensation reaction for 3.5 hours. Then removing nitrogen, adding tetrabutyl titanate, sealing, heating to about 220 ℃, starting polymerization reaction, and stopping stirring until the system in the three-neck flask is viscous and the micromolecule product (water) reaches a theoretical value to obtain a viscous product mixture. The prepared viscous product mixture material is taken out to be cooled, dissolved by chloroform and poured into alcohol to be separated out, and the hydrophilic modified PBS is prepared.
(2) Melting and blending the hydrophilic modified PBS and the insect pheromone at the temperature of 110 ℃ according to the mass ratio of (1: 0.30) to prepare composite master batches, and then blowing the composite master batches into a film at the temperature of 140 ℃ to prepare the biodegradable agricultural film containing the insect pheromone.
Example four:
a method for preparing a biodegradable agricultural film containing insect pheromone comprises the following raw material components: taking butanediol, succinic acid and a third monomer in a molar ratio of 1:1: 0.25; the amount of butyl titanate added as catalyst was 0.6% of the amount of butanediol or succinic acid material. The third monomer is 1,2, 4-benzenetriol, and the insect pheromone is as follows: (Z) -11-hexadecene aldehyde, (Z) -11-hexadecene-1-ol acetic acid, (Z) -11-hexadecene alcohol, (Z, E) -9, 12-tetradecadiene-1-ol acetate, and (Z) -9-tetradecene alcohol are compounded according to the mass ratio of (1: 1.1: 0.6: 1: 0.5).
The preparation process comprises the following steps:
(1) adding butanediol, succinic acid and a third monomer into a dry three-neck flask with a stirrer, introducing nitrogen and an elbow connecting pipe, stirring and heating to about 160 ℃, and starting a dehydration condensation reaction for 3.5 hours. Then removing nitrogen, adding tetrabutyl titanate, sealing, heating to about 220 ℃, starting polymerization reaction, and stopping stirring until the system in the three-neck flask is viscous and the micromolecule product (water) reaches a theoretical value to obtain a viscous product mixture. The prepared viscous product mixture material is taken out to be cooled, dissolved by chloroform and poured into alcohol to be separated out, and the hydrophilic modified PBS is prepared.
(2) Melting and blending the hydrophilic modified PBS and the insect pheromone at the temperature of 110 ℃ according to the mass ratio (1: 0.2) to prepare composite master batches, and then blowing the composite master batches into a film at the temperature of 140 ℃ to prepare the biodegradable agricultural film containing the insect pheromone.
Example five:
a method for preparing a biodegradable agricultural film containing insect pheromone comprises the following raw material components: taking butanediol, succinic acid and a third monomer in a molar ratio of 1:1: 0.25; the amount of butyl titanate added as catalyst was 0.6% of the amount of butanediol or succinic acid material. The third monomer is anhydrous phloroglucinol, and the insect pheromone is as follows: (Z) -11-hexadecene aldehyde, (Z) -11-hexadecene-1-ol acetic acid, (Z) -11-hexadecene alcohol, (Z, E) -9, 12-tetradecadiene-1-ol acetate, and (Z) -9-tetradecene alcohol are compounded according to the mass ratio of (1: 1.1: 0.8: 1: 0.4).
The preparation process comprises the following steps:
(1) adding butanediol, succinic acid and a third monomer into a dry three-neck flask with a stirrer, introducing nitrogen and an elbow connecting pipe, stirring and heating to about 170 ℃, and starting a dehydration condensation reaction for 3 hours. Then removing nitrogen, adding tetrabutyl titanate, sealing, heating to about 210 ℃, starting polymerization reaction, and stopping stirring until the system in the three-neck flask is viscous and the micromolecule product (water) reaches a theoretical value to obtain a viscous product mixture. The prepared viscous product mixture material is taken out to be cooled, dissolved by chloroform and poured into alcohol to be separated out, and the hydrophilic modified PBS is prepared.
(2) Melting and blending the hydrophilic modified PBS and the insect pheromone at the temperature of 110 ℃ according to the mass ratio of (1: 0.30) to prepare composite master batches, and then blowing the composite master batches into a film at the temperature of 140 ℃ to prepare the biodegradable agricultural film containing the insect pheromone.
Example six:
a method for preparing a biodegradable agricultural film containing insect pheromone comprises the following raw material components: taking butanediol, succinic acid and a third monomer in a ratio of 1:1: 0.3; the amount of butyl titanate added as catalyst was 0.8% of the amount of butanediol or succinic acid material. The third monomer is anhydrous phloroglucinol, and the insect pheromone is as follows: (Z) -11-hexadecene aldehyde, (Z) -11-hexadecene-1-ol acetic acid, (Z) -11-hexadecene alcohol, (Z, E) -9, 12-tetradecadiene-1-ol acetate, and (Z) -9-tetradecene alcohol are compounded according to the mass ratio of (1: 1.2: 0.6: 1: 0.5).
The preparation process comprises the following steps:
(1) adding butanediol, succinic acid and a third monomer into a dry three-neck flask with a stirrer, introducing nitrogen and an elbow connecting pipe, stirring and heating to about 170 ℃, and starting a dehydration condensation reaction for 3.5 hours. Then removing nitrogen, adding tetrabutyl titanate, sealing, heating to about 220 ℃, starting polymerization reaction, and stopping stirring until the system in the three-neck flask is viscous and the micromolecule product (water) reaches a theoretical value to obtain a viscous product mixture. The prepared viscous product mixture material is taken out to be cooled, dissolved by chloroform and poured into alcohol to be separated out, and the hydrophilic modified PBS is prepared.
(2) Melting and blending the hydrophilic modified PBS and the insect pheromone at the temperature of 110 ℃ according to the mass ratio of (1: 0.25) to prepare composite master batches, and then blowing the composite master batches into a film, wherein the film blowing temperature is controlled at 145 ℃ to prepare the biodegradable agricultural film containing the insect pheromone.
Example seven:
a method for preparing a biodegradable agricultural film containing insect pheromone comprises the following raw material components: taking butanediol, succinic acid and a third monomer in a ratio of 1:1: 0.15; the amount of butyl titanate added as catalyst was 0.3% of the amount of butanediol or succinic acid material. The third monomer is 1,4, 5-trihydroxy-2-pentanone, and the insect pheromone is: (Z) -11-hexadecene aldehyde, (Z) -11-hexadecene-1-ol acetic acid, (Z) -11-hexadecene alcohol, (Z, E) -9, 12-tetradecadiene-1-ol acetate, and (Z) -9-tetradecene alcohol are compounded according to the mass ratio of (0.5: 0.8: 0.5: 0.1).
The preparation process comprises the following steps:
(1) adding butanediol, succinic acid and a third monomer into a dry three-neck flask with a stirrer, introducing nitrogen and an elbow connecting pipe, stirring and heating to about 165 ℃, and starting a dehydration condensation reaction for 3.2 hours. Then removing nitrogen, adding tetrabutyl titanate, sealing, heating to about 215 ℃, starting polymerization reaction, and stopping stirring until the system in the three-neck flask is viscous and the micromolecule product (water) reaches a theoretical value to obtain a viscous product mixture. The prepared viscous product mixture material is taken out to be cooled, dissolved by chloroform and poured into alcohol to be separated out, and the hydrophilic modified PBS is prepared.
(2) Melting and blending the hydrophilic modified PBS and the insect pheromone at 115 ℃ according to the mass ratio of (1: 0.23) to prepare composite master batches, and then blowing the composite master batches into a film, wherein the film blowing temperature is controlled at 150 ℃ to prepare the biodegradable agricultural film containing the insect pheromone.
Example eight:
a method for preparing a biodegradable agricultural film containing insect pheromone comprises the following raw material components: taking butanediol, succinic acid and a third monomer in a ratio of 1:1: 0.17; the amount of butyl titanate added as catalyst was 0.4% of the amount of butanediol or succinic acid material. The third monomer is 1,3, 5-trihydroxy-2-bromobenzene, and the insect pheromone is: (Z) -11-hexadecene aldehyde, (Z) -11-hexadecene-1-ol acetic acid, (Z) -11-hexadecene alcohol, (Z, E) -9, 12-tetradecadiene-1-ol acetate, and (Z) -9-tetradecene alcohol are compounded according to the mass ratio of (0.3: 0: 0: 0.8: 0).
The preparation process comprises the following steps:
(1) adding butanediol, succinic acid and a third monomer into a dry three-neck flask with a stirrer, introducing nitrogen and an elbow connecting pipe, stirring and heating to about 165 ℃, and starting a dehydration condensation reaction for 3.3 hours. Then removing nitrogen, adding tetrabutyl titanate, sealing, heating to about 215 ℃, starting polymerization reaction, and stopping stirring until the system in the three-neck flask is viscous and the micromolecule product (water) reaches a theoretical value to obtain a viscous product mixture. The prepared viscous product mixture material is taken out to be cooled, dissolved by chloroform and poured into alcohol to be separated out, and the hydrophilic modified PBS is prepared.
(2) Melting and blending the hydrophilic modified PBS and the insect pheromone at the temperature of 120 ℃ according to the mass ratio of (1: 0.28) to prepare composite master batches, and then blowing the composite master batches into a film, wherein the film blowing temperature is controlled at 145 ℃ to prepare the biodegradable agricultural film containing the insect pheromone.
Example nine:
a method for preparing a biodegradable agricultural film containing insect pheromone comprises the following raw material components: taking butanediol, succinic acid and a third monomer in a ratio of 1:1: 0.27; the amount of butyl titanate added as catalyst was 0.7% of the amount of butanediol or succinic acid material. The third monomer is 2, 3, 4-trihydroxybenzaldehyde, and the insect pheromone is: (Z) -11-hexadecen-1-ol acetic acid.
The preparation process comprises the following steps:
(1) adding butanediol, succinic acid and a third monomer into a dry three-neck flask with a stirrer, introducing nitrogen and an elbow connecting pipe, stirring and heating to about 165 ℃, and starting a dehydration condensation reaction for 3.5 hours. Then removing nitrogen, adding tetrabutyl titanate, sealing, heating to about 215 ℃, starting polymerization reaction, and stopping stirring until the system in the three-neck flask is viscous and the micromolecule product (water) reaches a theoretical value to obtain a viscous product mixture. The prepared viscous product mixture material is taken out to be cooled, dissolved by chloroform and poured into alcohol to be separated out, and the hydrophilic modified PBS is prepared.
(2) Melting and blending the hydrophilic modified PBS and the insect pheromone at the temperature of 120 ℃ according to the mass ratio of (1: 0.25) to prepare composite master batches, and then blowing the composite master batches into a film, wherein the film blowing temperature is controlled at 145 ℃ to prepare the biodegradable agricultural film containing the insect pheromone.
The degradation rate of the biodegradable agricultural film containing the insect pheromone prepared in the embodiments 1 to 6 of the invention and the control effect of prodenia litura, beet armyworm and diamond back moth in the greenhouse are tested, and the specific experimental data are shown in tables 1 and 2.
(1) Degradation rate test of biodegradable agricultural film containing insect pheromone
Simulated natural degradation test: mixing natural soil with water at a mass ratio of 1:5, stirring for 24h, standing for 24h, and collecting supernatant as degradation liquid. Cutting the composite materials with different proportions into samples with the size of 25mm multiplied by 0.6mm, accurately weighing after vacuum drying, putting the samples into a centrifuge tube filled with degradation liquid, putting the centrifuge tube into a shaking table to simulate the natural degradation process, and sampling once every 30 days. And repeatedly washing the obtained sample with distilled water, drying to constant weight, weighing, and calculating the mass loss rate of the degraded sample. Each group of 3 replicates were averaged. The degradation rate of the material is calculated by the formula:
Figure BDA0003033536090000121
in the formula: m-mass loss rate (%) of the sample; m is0-the original mass (g) of the sample; m is1Mass (g) of the sample after degradation.
TABLE 1 degradation rate test result of biodegradable greenhouse agricultural film containing insect pheromone
Degradation rate/month 1 2 3 4 5 6
Example 1 0~10.3% 10.3%~26.3% 26.3%~37.3% 37.3%~49.6% 49.6%~56.8% 56.8%~67.4%
Example 2 0~11.5% 11.5%~27.6% 27.6%~38.9% 38.9%~50.2% 50.2%~58.4% 58.4%~66.9%
Example 3 0~11.7% 11.7%~28.2% 28.2%~41.7% 41.7%~53.5% 53.5%~62.1% 62.1%~71.3%
Example 4 0~10.8% 10.8%~27.1% 27.1%~36.5% 36.5%~51.5% 51.5%~57.8% 57.8%~63.1%
Example 5 0~12.1% 12.1%~28.3% 28.3%~39.7% 39.7%~52.9% 52.9%~61.4% 61.4%~68.2%
Example 6 0~11.2% 11.2%~26.9% 26.9%~38.6% 38.6%~49.5% 49.5%~57.4% 57.4%~64.9%
Example 7 0~10.6% 10.6%~27.4% 27.4%~36.9% 36.9%~51.5% 51.5%~58.6% 58.6%~68.9%
Example 8 0~11.3% 11.3%~28.7% 28.7%~42.3% 42.3%~52.1% 52.1%~62.5% 62.5%~70.8%
Example 9 0~12.3% 12.3%~27.3% 27.3%~40.2% 40.2%~53.7% 53.7%~63.1% 63.1%~69.2%
(2) Calculation of control Effect of biodegradable agricultural film containing insect pheromone
Disorientation rate: after the biodegradable agricultural film containing the insect pheromone is adopted, a sex-trap for monitoring is arranged in the disorientation control area and the comparison area to count the number of male moths in the shed, and the sex-trap is used for calculating the moth decline rate to reflect the mating interference effect of the shed film containing the biological pheromone on male and female.
The disorientation ratio (%) (number of moths in 1-treated area/number of moths in control area) × 100%
TABLE 2 prevention and control effect test of biodegradable greenhouse agricultural film containing insect pheromone
Figure BDA0003033536090000122
Figure BDA0003033536090000131
In summary, the invention discloses a preparation method of a biodegradable agricultural film containing insect pheromone, which comprises the following raw materials: butanediol, succinic acid, a hydrophilic third monomer, butyl titanate and insect pheromone. Wherein the molar mass ratio of the butanediol to the succinic acid to the hydrophilic third monomer is 1:1 (0.15-0.30); butyl titanate is 0.03 to 0.08 percent of the molar mass of the polymer monomer; the mass ratio of PBS to insect pheromone is 1: (0.2-0.3). The preparation method comprises the steps of carrying out dehydration condensation on each reaction raw material, heating, polymerizing and purifying, and then blending at 130-150 ℃ to prepare the biodegradable agricultural film containing the insect pheromone, wherein the prepared biodegradable agricultural film containing the insect pheromone has a good insect pest control function on the premise of keeping the material biodegradable, and can be used for green agriculture and insect pest control.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (10)

1. A preparation method of a biodegradable agricultural film containing insect pheromone is characterized in that hydrophilic modified PBS and the insect pheromone are melted and blended to prepare composite master batches, and the obtained composite master batches are subjected to a film blowing process to prepare the biodegradable agricultural film containing the insect pheromone.
2. The method of claim 1, wherein the insect pheromone comprises: at least one of (Z) -11-hexadecenal, (Z) -11-hexadecen-1-ol acetic acid, (Z) -11-hexadecenol, (Z, E) -9, 12-tetradecadiene-1-ol acetate, and (Z) -9-tetradecenol.
3. The method for preparing a biodegradable agricultural film containing insect pheromone according to claim 2, wherein (Z) -11-hexadecenal, (Z) -11-hexadecen-1-ol acetic acid, (Z) -11-hexadecenol, (Z, E) -9, 12-tetradecadiene-1-ol acetate, (Z) -9-tetradecenol are compounded in a mass ratio of 0-1: 0-1.2: 0-0.8: 0-1: 0-0.5, wherein at least one of the mass ratios is not zero.
4. The method for preparing the biodegradable agricultural film containing the insect pheromone as claimed in claim 1, wherein the mixing mass ratio of the hydrophilic modified PBS to the insect pheromone is 1: 0.2-0.3.
5. The method for preparing a biodegradable agricultural film containing insect pheromone according to claim 1, wherein the temperature of melt blending is 110-120 ℃, and the temperature of the film blowing process is 130-150 ℃.
6. The method for preparing a biodegradable agricultural film containing insect pheromone as set forth in claim 1, wherein the hydrophilic modified PBS is prepared by the following steps:
uniformly mixing butanediol, succinic acid and a third monomer, performing dehydration condensation reaction to obtain a reaction mixture, adding butyl titanate into the obtained reaction mixture to perform polymerization reaction to obtain a viscous product mixture, cooling the obtained viscous product mixture, and removing impurities to obtain hydrophilic modified PBS;
wherein, the third monomer is polyhydroxy hydrophilic monomer.
7. The method of claim 6, wherein the hydrophilic polyhydroxy monomer is glycerol, trihydroxymethyl propane, trimethylolethane, anhydrous phloroglucinol, phloroglucinol dihydrate, 1,2, 4-benzenetriol, 2, 3, 4-trihydroxybenzaldehyde, 1,4, 5-trihydroxy-2-pentanone, or 1,3, 5-trihydroxy-2-bromobenzene.
8. The method for preparing a biodegradable agricultural film containing insect pheromone according to claim 6, wherein the molar ratio of the butanediol, the succinic acid and the third monomer is 1:1: 0.15-0.30; the butyl titanate is 0.3-0.8% of the butanediol.
9. The method for preparing a biodegradable agricultural film containing insect pheromone according to claim 6, wherein the temperature of the dehydration condensation reaction is 160-170 ℃ and the time is 3-3.5 h;
the temperature of the polymerization reaction is 210-220 ℃.
10. A biodegradable agricultural film containing insect pheromone prepared by the method of any one of claims 1 to 9.
CN202110437277.0A 2021-04-22 2021-04-22 Insect pheromone-containing biodegradable agricultural film and preparation method thereof Pending CN113121965A (en)

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