AU2021104356A4 - A Degradable Composite Film With The Effect Of Pesticide Adsorption Based On The Metal-Organic Framework Material - Google Patents
A Degradable Composite Film With The Effect Of Pesticide Adsorption Based On The Metal-Organic Framework Material Download PDFInfo
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- AU2021104356A4 AU2021104356A4 AU2021104356A AU2021104356A AU2021104356A4 AU 2021104356 A4 AU2021104356 A4 AU 2021104356A4 AU 2021104356 A AU2021104356 A AU 2021104356A AU 2021104356 A AU2021104356 A AU 2021104356A AU 2021104356 A4 AU2021104356 A4 AU 2021104356A4
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- 239000000575 pesticide Substances 0.000 title claims abstract description 87
- 239000000463 material Substances 0.000 title claims abstract description 53
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 30
- 230000000694 effects Effects 0.000 title claims abstract description 18
- 239000013132 MOF-5 Substances 0.000 claims abstract description 40
- 239000007921 spray Substances 0.000 claims abstract description 40
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 29
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 29
- 229920002472 Starch Polymers 0.000 claims abstract description 28
- 239000008107 starch Substances 0.000 claims abstract description 28
- 235000019698 starch Nutrition 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- -1 i.e. Substances 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 22
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 238000005507 spraying Methods 0.000 claims description 11
- 229940057499 anhydrous zinc acetate Drugs 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000011550 stock solution Substances 0.000 claims description 10
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 10
- 235000011187 glycerol Nutrition 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000010096 film blowing Methods 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 1
- 238000004729 solvothermal method Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 239000002689 soil Substances 0.000 abstract description 10
- 238000011161 development Methods 0.000 abstract description 3
- 241000196324 Embryophyta Species 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract description 2
- 238000013268 sustained release Methods 0.000 description 19
- 239000012730 sustained-release form Substances 0.000 description 19
- 238000006065 biodegradation reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000009864 tensile test Methods 0.000 description 5
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000013259 porous coordination polymer Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/24—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients to enhance the sticking of the active ingredients
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
- A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
- A01N43/70—Diamino—1,3,5—triazines with only one oxygen, sulfur or halogen atom or only one cyano, thiocyano (—SCN), cyanato (—OCN) or azido (—N3) group directly attached to a ring carbon atom
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- C08J2329/00—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 at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic 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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Manufacturing & Machinery (AREA)
- Toxicology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
of Descriptions
The present invention relates to the field of new agricultural film materials, particularly to
providing a degradable composite film with the effect of pesticide adsorption based on the
metal-organic framework material and its preparation method, which uses the metal-organic
framework material, i.e., MOF-5, as the adsorption carrier of pesticide, and takes the composite film
made of polyvinyl alcohol and starch as the base material, and thus makes the metal-organic
framework material carrying pesticides be adsorbed on the surface of the degradable composite film
by means of the electrostatic spray technology, so that it can play functions of preservation of soil
moisture, increasing temperature, and suppressing weeds, and thus is of important and profound
significance for the development of green agriculture in future.
Description
Descriptions A Degradable Composite Film with the Effect of Pesticide Adsorption Based on the Metal-Organic Framework Material
Technical Field The present invention relates to the field of new agricultural film materials, particularly to a degradable composite film with the effect of pesticide adsorption based on the metal-organic framework material and its preparation method.
Background Technology Nowadays, the utilization of agricultural film and pesticides in agricultural production has been translated into a leap in agricultural productivity and resulted in change in production methods. However, the chemical compositions of traditional agricultural film are mainly polyethylene or polyvinyl chloride, which cannot be degraded in the soil under natural conditions. The long-term residue agricultural film would be aged and hardened, which may destroy the soil structure of the plough layer, block the conduction of soil, water and fertilizer, so as to reduce the activity of microorganisms in the soil, and make the drought resistance capacity of the soil decline, which causes an adverse effect on the production capacity of the land and the sustainable development of agriculture. For the purpose of reducing the adverse effect of pesticides on the environment through immediate contact of the soil, various types of sustained-release films have been developed, such as a sustained-release film for pesticides which is prepared by using the blend of polyvinyl alcohol and starch as raw material and taking halloysite nanotubes and montmorillonite as carriers of pesticides. A great deal studies on sustained-release films would be conducive to improving the utilization of pesticides, and thus reducing the damage of pesticides to the land to a certain extent. Metal-organic frameworks (MOFs) refer to porous coordination polymer materials with three-dimensional periodic network structure which are formed by connection of secondary structural units composed of inorganic metal ions and oxygenated or nitrogenous organic ligands through strong chemical bonds. Based upon the characteristics of the chemical compositions, MOFs materials have the properties of organic and inorganic materials, also have high specific surface area, high porosity and excellent thermal stability, and the structure of which can be controlled and designed through the targeted design of topological structure and the expansion of organo-functional groups. Thus, MOFs materials attracted more and more attention from fields of gas separation, energy storage, catalysis, and adsorption, and have been widely applied. Due to there are abundant active sites existed in the pore channels of molecules, the studies and the
Descriptions application of MOFs materials in the field of adsorption has been increasing recently. However, relevant studies on the adsorption of MOFs materials to molecules of pesticides are rarely reported. The electrostatic spray method belongs to a kind of electrostatic spinning. The principle of which is based on the working principle of electro-hydrodynamics, and can be carried out by using polymer melts or polymer solution. By contrast, due to there is no existence of organic solvent and the process is simple, the electrostatic spray method is more economical and environmentally friendly. In addition, relevant studies on electrostatic spray have being carried out and such method has been applied in several fields of biomedical engineering, such as drug delivery, biological sensor, tissue engineering and regenerative medicine. In conclusion, in terms of the application of traditional agricultural films and pesticides, there are two urgent problems need to be solved: (1) traditional agricultural films are non-degradable, and the residue plastic films remained in the soil would impede the growth of crops and affect the absorption of nutrients and water by crops, and thus reduce the crop yield; (2) there is no suitable adsorption material to control the release of pesticides. Thus, finding a way to solve the aforesaid problems has become a tough problem of this field.
Summary of the Present Invention Aiming at those deficiencies existed in the prior art, the present invention provides a degradable composite film with the effect of pesticide adsorption based on the metal-organic framework material and its preparation method, which uses the metal-organic framework material, i.e., MOF-5, as the adsorption carrier of pesticide, and takes the composite film made of polyvinyl alcohol and starch as the base material, and thus makes the metal-organic framework material carrying pesticides be adsorbed on the surface of the composite film by means of the electrostatic spray technology, so that it can play functions of preservation of soil moisture, increasing temperature, and suppressing weeds. Compared with traditional administration methods, such method can reduce the hazard caused by pesticides through immediate contact effectively, and has better biocompatibility compared with other sustained-release films. In addition, the large specific surface area of metal-organic framework material can increase the adsorption capacity of pesticides, and thus make use of the pesticide adsorbents to the full extent, furthermore, the decomposed products of metal-organic framework material are beneficial to the growth of plants. Thus, the present invention is of important and profound significance for the development of green agriculture in future. The specific technical scheme of the present invention is: A degradable composite film with the effect of pesticide adsorption based on the metal-organic
Descriptions framework material, which is composed of a degradable biological film and a metal-organic framework material carrying pesticides, which is adsorbed on the surface of the degradable biological film; The said metal-organic framework material is MOF-5; The said degradable composite film is made of polyvinyl alcohol and starch; The said metal-organic framework material carrying pesticides is adsorbed on the surface of the degradable composite film by means of the electrostatic spray technology; The preparation method of the metal-organic framework material, i.e., MOF-5 is as follows: Take 3-4 parts of anhydrous zinc acetate, 1 part of terephthalic acid, and 100-200ml of DMF; Disperse the anhydrous zinc acetate and the terephthalic acid in the DMF for 10-15 minutes by an ultrasonic oscillator; Transfer the obtained mixed solution into a clean reaction kettle with polytetrafluoroethylene; Place the reaction kettle in the oven to react for 24-30 hours at the temperature of 120°C; Centrifuge the obtained reactant at the speed of 5800-6800 rpm for 10 minutes, and then wash it with DMF repeatedly for 3-5 times; Place the centrifuged product in a vacuum drier to dry for 12-14 hours, and thus obtain the MOF-5. The preparation method of the degradable biological film is as follows: The compositions of raw materials measured in parts by weight include: 65-75 parts of polyvinyl alcohol, 15-20 parts of starch, 5-10 parts of plasticizer, and 5-10 parts of compatibilizer; Wherein, the said plasticizer can be one of glycerin, polyethylene glycol, pentaerythritol, xylitol, mannitol, 1,2,6-hexanetriol, 1,4-butanediol, and the compatibilizer can be one of citric acid and aluminum hydroxide. Weigh the raw materials according to the aforesaid compositions, and mix the polyvinyl alcohol with the starch, the plasticizer, the compatible modifier, and other additives in a high-speed mixer for 10-15 minutes; Blend, extrude and granulate the obtained mixture system directly by a screw extruder at the temperature of 120°C-150°C, and thus obtain the composite material of polyvinyl alcohol/starch; Obtain the 30-40um of degradable biological film through extrusion and film blowing of the composite material of polyvinyl alcohol/starch. The preparation method of the said MOF-5 carrying pesticides is as follows: Disperse 0.2g of MOF-5 in the atrazine/chloroform solution with a concentration of 0.006g/L-0.03g/L;
Descriptions Place the mixed solution in a thermostatic shaking incubator, and control the temperature at °C-65°C, wherein, the adsorption time should be 24-72 hours; Centrifuge the aforesaid obtained reactant at the speed of 5800-6800 rpm for 10-15 minutes, and then dry the obtained product for 24 hours, and thus obtain the MOF-5 carrying pesticides. The specific process of making the MOF-5 carrying pesticides be adsorbed on the surface of the degradable biological film is as follows: Prepare the stock solution of electrostatic spray: disperse the MOF-5 carrying pesticides in methyl alcohol according to the mass fraction of 10%-15%, and thus obtain the stock solution of spray, wherein, the dispersion time should be 6-8 hours; Regulate the process parameters of the TYDO1 electrostatic sprayer: wherein, the spraying conditions should be controlled as follows: the temperature is at 25°C-35°C, the spray voltage is -15kv, the flow velocity of spray solution is 1-10ml, and the spray receiving distance is 10-15cm, in addition, the electrode rotating speed of receiving roller is 500-1000rpm, and the back and forth running speed of needle is 30-50cm/min, as well as the spraying time is 24-36 hours; Dry it under natural conditions, and thus obtain the uniformly distributed sustained-release film of pesticide. Compared with the prior art, the advantages of the present invention include: (1) The main compositions of the degradable biological film utilized by the present invention are polyvinyl alcohol and starch. Wherein, the polyvinyl alcohol (PVA) film has outstanding advantages in terms of water solubility and degradability, etc., and the starch is a natural high molecular material which has wide sources and is at low-cost; thus, adding starch to polyvinyl alcohol can not only reduce the cost greatly, but also facilitate the biodegradation of the film, and thus improve the degradability of the film. (2) The adsorption material utilized by the present invention is a metal-organic framework, i.e., MOF-5, which has a large pore size and good adsorption property, so that it can effectively make pesticides be adsorbed into the pores, and thus reduce the direct harm of pesticides to the soil. (3) The electrostatic spray technology adopted by the present invention, which can make the MOF-5 carrying pesticides be adsorbed on the surface of the substrate of degradable biological film, will not affect the structural stability of the film. (4) Compared with the traditional sustained-release film of pesticide, the selected adsorbent is a metal-organic framework material, and the final decomposed product of which contains zinc element, so that it is conducive to the growth of crops.
Detailed Description of the Presently Preferred Embodiments
Descriptions For the purpose of making the advantages and features of the present invention can be more easily understood by those skilled in the art, and thus determining the protection scope of the present invention more clearly and definitely, the text below will describe the present invention in detail in conjunction with preferred embodiments. Unless otherwise specified, all elements used fall within existing technologies;
Embodiment 1 Prepare the metal-original framework material: (1) Weigh 0.66g of anhydrous zinc acetate and 0.20g of terephthalic acid; (2) Measure 100ml of DMF, and disperse the anhydrous zinc acetate and the terephthalic acid in the DMF for 10 minutes by an ultrasonic oscillator; (3) Transfer the obtained mixed solution into a clean reaction kettle with polytetrafluoroethylene; (4) Place the reaction kettle in the oven to react for 24 hours at the temperature of 120°C; (5) Centrifuge the obtained reactant at the speed of 5800 rpm for 10 minutes, and then wash it with DMF repeatedly for 3 times; (6) Place the centrifuged product in a vacuum drier to dry for 12 hours, and thus obtain the MOF-5. Prepare the degradable biological film: (1) Weigh 65g of polyvinyl alcohol, 15g of starch, 5g of glycerin, and 5g of citric acid; (2) Mix the polyvinyl alcohol with starch, the glycerin, the citric acid, and the water in a high-speed mixer for 10 minutes; (3) Blend, extrude and granulate the obtained mixture system directly by a screw extruder at the temperature of 120°C-150°C, and thus obtain the composite material of polyvinyl alcohol/starch; (4) Obtain the 40um of degradable biological film through extrusion and film blowing of the composite material of polyvinyl alcohol/starch. Prepare the MOF-5 carrying pesticides: (1) Weigh 0.2g of MOF-5, and measure 30ml of pesticide/chloroform solution with a concentration of 0.03g/L; (2) Disperse 0.2g of MOF-5 in the atrazine/chloroform solution with a concentration of 0.03g/L; (3) Place the mixed solution in a thermostatic shaking incubator, and control the temperature at °C, wherein, the adsorption time should be 36 hours;
Descriptions (4) Centrifuge the aforesaid obtained mixture at the speed of 5800 rpm for 10 minutes; (5) Dry the obtained product for 24 hours, and thus obtain the MOF-5 carrying pesticides. Prepare the sustained-release film of pesticide by means of the electrostatic spray method: (1) Prepare the stock solution of electrostatic spray: weigh 20g of MOF-5 carrying pesticides, and then disperse them in 20g of methyl alcohol, and thus obtain the stock solution of spray, wherein, the dispersion time should be 6 hours; (2) Regulate the process parameters of the TYDO1 electrostatic sprayer: wherein, the spraying conditions should be controlled as follows: the temperature is at 30°C, the spray voltage is 12kv, the flow velocity of spray solution is 8[L/min, and the spray receiving distance is 10-15cm, in addition, the electrode rotating speed of receiving roller is 800rpm, and the back and forth running speed of needle is 35cm/min, as well as the spraying time is 24 hours; (3) Dry it under natural conditions, and thus obtain the uniformly distributed sustained-release film of pesticide. The tensile strength of the sustained-release film of pesticide prepared by this method after the tensile test of the film is 28.5MPa, and the elongation at break is 356%, thefilm thickness is 38um, and the releasing time of pesticide is 68d, as well as the biodegradation rate within 45d is 52%.
Comparative Example 1 The difference between this comparative example and the embodiment 1 is that the preparation of the MOF-5 carrying pesticides was omitted, and during the process of preparing the sustained-release film of pesticide by means of the electrostatic spray method, the MOF-5 carrying pesticides was replaced by pesticide, and the rest of the steps were unchanged. The tensile strength of the sustained-release film of pesticide prepared by this method after the tensile test of the film is 29.5MPa, and the elongation at break is 372%, thefilm thickness is 37um, and the releasing time of pesticide is 45d, as well as the biodegradation rate within 45d is 49%.
Comparative Example 2 The difference between this comparative example and the embodiment 1 is that the preparation of the MOF-5 carrying pesticides was omitted, and during the process of preparing the sustained-release film of pesticide by means of the electrostatic spray method, the MOF-5 carrying pesticides was replaced by the MOF-5, and the rest of the steps were unchanged. The tensile strength of the sustained-release film of pesticide prepared by this method after the tensile test of the film is 28.5MPa, and the elongation at break is 364%, the film thickness is 35um, and the releasing time of pesticide is Od, as well as the biodegradation rate within 45d is 51%.
Descriptions
Embodiment 2 Prepare the metal-original framework material: (1) Weigh 0.66g of anhydrous zinc acetate and 0.20g of terephthalic acid; (2) Measure 100ml of DMF, and disperse the anhydrous zinc acetate and the terephthalic acid in the DMF for 10 minutes by an ultrasonic oscillator; (3) Transfer the obtained mixed solution into a clean reaction kettle with polytetrafluoroethylene; (4) Place the reaction kettle in the oven to react for 24 hours at the temperature of 120°C; (5) Centrifuge the obtained reactant at the speed of 5800 rpm for 10 minutes, and then wash it with DMF repeatedly for 3 times; (6) Place the centrifuged product in a vacuum drier to dry for 12 hours, and thus obtain the MOF-5. Prepare the degradable biological film: (1) Weigh 65g of polyvinyl alcohol, 15g of starch, 5g of glycerin, and 5g of citric acid; (2) Mix the polyvinyl alcohol with starch, the glycerin, the citric acid, and the water in a high-speed mixer for 10 minutes; (3) Blend, extrude and granulate the obtained mixture system directly by a screw extruder at the temperature of 120°C-150°C, and thus obtain the composite material of polyvinyl alcohol/starch; (4) Obtain the 40um of degradable biological film through extrusion and film blowing of the composite material of polyvinyl alcohol/starch. Prepare the MOF-5 carrying pesticides: (1) Weigh 0.2g of MOF-5, and measure 30ml of pesticide/chloroform solution with a concentration of 0.02g/L; (2) Disperse 0.2g of MOF-5 in the atrazine/chloroform solution with a concentration of 0.02g/L; (3) Place the mixed solution in a thermostatic shaking incubator, and control the temperature at °C, wherein, the adsorption time should be 36 hours; (4) Centrifuge the aforesaid obtained mixture at the speed of 5800 rpm for 10 minutes; (5) Dry the obtained product for 24 hours, and thus obtain the MOF-5 carrying pesticides. Prepare the sustained-release film of pesticide by means of the electrostatic spray method: (1) Prepare the stock solution of electrostatic spray: weigh 20g of MOF-5 carrying pesticides, and then disperse them in 20g of methyl alcohol, and thus obtain the stock solution of spray,
Descriptions wherein, the dispersion time should be 6 hours; (2) Regulate the process parameters of the TYDO1 electrostatic sprayer: wherein, the spraying conditions should be controlled as follows: the temperature is at 30°C, the spray voltage is 12kv, the flow velocity of spray solution is 8L/min, and the spray receiving distance is 10 cm, in addition, the electrode rotating speed of receiving roller is 800rpm, and the back and forth running speed of needle is 35cm/min, as well as the spraying time is 24 hours; (3) Dry it under natural conditions, and thus obtain the uniformly distributed sustained-release film of pesticide. The tensile strength of the sustained-release film of pesticide prepared by this method after the tensile test of the film is 28.5MPa, and the elongation at break is 356%, the film thickness is 36um, and the releasing time of pesticide is 52d, as well as the biodegradation rate within 45d is 58%.
Embodiment 3 Prepare the metal-original framework material: (1) Weigh 0.66g of anhydrous zinc acetate and 0.20g of terephthalic acid; (2) Measure 100ml of DMF, and disperse the anhydrous zinc acetate and the terephthalic acid in the DMF for 10 minutes by an ultrasonic oscillator; (3) Transfer the obtained mixed solution into a clean reaction kettle with polytetrafluoroethylene; (4) Place the reaction kettle in the oven to react for 24 hours at the temperature of 120°C; (5) Centrifuge the obtained reactant at the speed of 5800 rpm for 10 minutes, and then wash it with DMF repeatedly for 3 times; (6) Place the centrifuged product in a vacuum drier to dry for 12 hours, and thus obtain the MOF-5. Prepare the degradable biological film: (1) Weigh 65g of polyvinyl alcohol, 15g of starch, 5g of glycerin, and 5g of citric acid; (2) Mix the polyvinyl alcohol with starch, the glycerin, the citric acid, and the water in a high-speed mixer for 10 minutes; (3) Blend, extrude and granulate the obtained mixture system directly by a screw extruder at the temperature of 120°C, and thus obtain the composite material of polyvinyl alcohol/starch; (4) Obtain the 40um of degradable biological film through extrusion and film blowing of the composite material of polyvinyl alcohol/starch. Prepare the MOF-5 carrying pesticides: (1) Weigh 0.2g of MOF-5, and measure 30ml of pesticide/chloroform solution with a
Descriptions concentration of 0.01g/L; (2) Disperse 0.2g of MOF-5 in the atrazine/chloroform solution with a concentration of 0.01g/L; (3) Place the mixed solution in a thermostatic shaking incubator, and control the temperature at °C, wherein, the adsorption time should be 36 hours; (4) Centrifuge the aforesaid obtained mixture at the speed of 5800 rpm for 10 minutes; (5) Dry the obtained product for 24 hours, and thus obtain the MOF-5 carrying pesticides. Prepare the sustained-release film of pesticide by means of the electrostatic spray method: (1) Prepare the stock solution of electrostatic spray: weigh 20g of MOF-5 carrying pesticides, and then disperse them in 20g of methyl alcohol, and thus obtain the stock solution of spray, wherein, the dispersion time should be 6 hours; (2) Regulate the process parameters of the TYDO1 electrostatic sprayer: wherein, the spraying conditions should be controlled as follows: the temperature is at 30°C, the spray voltage is 12kv, the flow velocity of spray solution is 8[L/min, and the spray receiving distance is 10-15cm, in addition, the electrode rotating speed of receiving roller is 800rpm, and the back and forth running speed of needle is 35cm/min, as well as the spraying time is 24 hours; (3) Dry it under natural conditions, and thus obtain the uniformly distributed sustained-release film of pesticide. The tensile strength of the sustained-release film of pesticide prepared by this method after the tensile test of the film is 28.5MPa, and the elongation at break is 356%, the film thickness is 37um, and the releasing time of pesticide is 42d, as well as the biodegradation rate within 45d is 53%.
Claims (14)
1. A degradable composite film with the effect of pesticide adsorption based on the metal-organic framework material, characterized in that being composed of a degradable biological film and a metal-organic framework material carrying pesticides, which is adsorbed on the surface of the degradable biological film;
2. The said degradable composite film with the effect of pesticide adsorption based on the metal-organic framework material according to Claim 1, characterized in that the selected metal-organic framework is one of Zr-type MOFs or Zn-type MOFs;
3. The said degradable composite film with the effect of pesticide adsorption based on the metal-organic framework material according to Claim 1, characterized in that the said degradable composite film is made of polyvinyl alcohol and starch;
4. The said degradable composite film with the effect of pesticide adsorption based on the metal-organic framework material according to Claim 1, characterized in that: the metal-organic framework material carrying pesticides is adsorbed on the surface of the degradable composite film by means of the electrostatic spray technology;
5. The said preparation method of the degradable composite film with the effect of pesticide adsorption based on the metal-organic framework material according to Claims 1-4, which consists of preparing a metal-organic framework material, preparing a metal-organic framework material carrying pesticides, preparing a degradable composite film, and preparing a degradable composite film with the effect of pesticide adsorption based on the metal-organic framework material;
6. The said preparation method of the metal-organic framework material according to Claim 5, characterized in that: the said metal-organic framework material is prepared through Zn (CH 3 COO) 2 and terephthalic acid by means of solvothermal method;
7. The said preparation method of the metal-organic framework material according to Claim 5, characterized in that: the said metal-organic framework material carrying pesticides is adsorbed in the metal-organic framework material by means of adsorption;
8. The said preparation method of the degradable composite film according to Claim 5, characterized in that: the said degradable composite film is obtained by means of the melt extrusion method;
9. The said preparation method of the degradable composite film according to Claim 5, characterized in that: the said degradable composite film with the effect of pesticide adsorption based on the metal-organic framework material is obtained by using the electrostatic spray technology;
10. The said preparation method of the metal-organic framework material according to Claim 6, characterized in that:
Claims The compositions of raw materials measured in parts by weight include: 3-4 parts of anhydrous zinc acetate, 1 part of terephthalic acid, and 100-200ml of DMF; Dispersing the anhydrous zinc acetate and the terephthalic acid in the DMF for 10-15 minutes by an ultrasonic oscillator; Transferring the obtained mixed solution into a clean reaction kettle with polytetrafluoroethylene; Placing the reaction kettle in the oven to react for 24-30 hours at the temperature of 120-130°C; Centrifuging the obtained reactant at the speed of 5800-6800 rpm for 10-15 minutes, and then washing it with DMF repeatedly for 3-5 times; Placing the centrifuged product in a vacuum drier to dry for 12-14 hours, and thus obtaining the MOF-5.
11. The said preparation method of the metal-organic framework material carrying pesticides according to Claim 7, characterized in that: dispersing 0.2g of MOF-5 in a pesticide/chloroform solution with a concentration of 0.006g/L-0.03g/L; Placing the mixed solution in a thermostatic shaking incubator, and controlling the temperature at 30°C-65°C, wherein, the adsorption time should be 24-72 hours; Centrifuging the obtained mixture, and then drying it for 24-36 hours, and thus obtaining the MOF-5 carrying pesticides.
12. The said preparation method of the degradable composite film carrying pesticides according to Claim 8, characterized in that: The preparation process of the said degradable composite film is as follows: The compositions of raw materials measured in parts by weight include: 65-75 parts of polyvinyl alcohol, 15-20 parts of starch, 5-10 parts of plasticizer, and 5-10 parts of compatibilizer; Wherein, the said plasticizer can be one of glycerin, polyethylene glycol, pentaerythritol, xylitol, mannitol, 1,2,6-hexanetriol, 1,4-butanediol, and the compatibilizer can be one of citric acid and aluminum hydroxide. Weighing the raw materials according to the aforesaid compositions, and mixing the polyvinyl alcohol with the starch, the plasticizer, the compatible modifier, and other additives in a high-speed mixer for 10-15 minutes; Blending, extruding and granulating the obtained mixture system directly by a screw extruder at the temperature of 120°C-150°C, and thus obtaining a composite material of polyvinyl alcohol/starch; Obtaining the degradable biological film through extrusion and film blowing of the composite
Claims material of polyvinyl alcohol/starch.
13. The said degradable composite film with the effect of pesticide adsorption based on the metal-organic framework material according to Claim 9, characterized in that the specific process of making the MOF-5 carrying pesticides be adsorbed on the surface of the degradable biological film is as follows: Prepare the stock solution of electrostatic spray: disperse the MOF-5 carrying pesticides in methyl alcohol according to the mass fraction of 10%-15%, and thus obtain the stock solution of spray, wherein, the dispersion time should be 6-8 hours; Regulate the process parameters of the electrostatic sprayer: wherein, the spraying conditions should be controlled as follows: the temperature is at 25°C-35°C, the spray voltage is 10-15kv, the flow velocity of spray solution is 1-10ul/min, and the spray receiving distance is 10-15cm, in addition, the electrode rotating speed of receiving roller is 500-1000rpm, and the back and forth running speed of needle is 30-50cm/min, as well as the spraying time is 24-36 hours; After spraying, dry it under natural conditions, and thus obtain the degradable composite film with effect of pesticide adsorption based on the metal-organic framework material.
14. The model of the instrument utilized by the said electrostatic spray method according to Claim 12 is TYDO1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116396496A (en) * | 2023-05-19 | 2023-07-07 | 安徽建筑大学 | Molecularly imprinted Zr-MOF fluorescent probe material and preparation method and application thereof |
| CN116941612A (en) * | 2023-09-21 | 2023-10-27 | 江西联普人农业科技有限公司 | Pesticide residue degradation agent and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116396496A (en) * | 2023-05-19 | 2023-07-07 | 安徽建筑大学 | Molecularly imprinted Zr-MOF fluorescent probe material and preparation method and application thereof |
| CN116941612A (en) * | 2023-09-21 | 2023-10-27 | 江西联普人农业科技有限公司 | Pesticide residue degradation agent and preparation method thereof |
| CN116941612B (en) * | 2023-09-21 | 2023-12-29 | 江西联普人农业科技有限公司 | Pesticide residue degradation agent and preparation method thereof |
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