CN112279729A - Special anion response controlled-release membrane material for saline-alkali soil and preparation method thereof - Google Patents

Special anion response controlled-release membrane material for saline-alkali soil and preparation method thereof Download PDF

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CN112279729A
CN112279729A CN202011250614.7A CN202011250614A CN112279729A CN 112279729 A CN112279729 A CN 112279729A CN 202011250614 A CN202011250614 A CN 202011250614A CN 112279729 A CN112279729 A CN 112279729A
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saline
acid
parts
anion
alkali soil
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胡树文
刘晋
高子登
许紫峻
任雪芹
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China Agricultural University
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China Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/30—Layered or coated, e.g. dust-preventing coatings

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  • Pest Control & Pesticides (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Fertilizers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)

Abstract

The invention provides a special controlled-release membrane material for saline-alkali soil, which is prepared from the following raw materials in parts by weight: 300-1000 parts of organic polymer material, 300-2000 parts of organic solvent, 0.05-5 parts of catalyst, 0.05-2 parts of cross-linking agent, 0-20 parts of anion response material and 100-1000 parts of distilled water; the organic polymer material comprises chitin and polyamino acid; wherein the mass ratio of the chitin to the polyamino acid is 1-5: 1. the added anion response material is taken as alkali-resistant monomer and combined into the polymer system through hydrogen bond action, the adding proportion is changed, and the Cl which causes the alkalinity to be increased in different types of soil‑、HCO3 ‑、CO3 2‑、SO4 2‑The ions are subjected to precipitation reaction, anions in the soil are passivated, the transmittance of materials in the film is slowed down, and meanwhile, the total salt content of the soil is reduced when the water enters the position below a plough layer along with irrigation water.

Description

Special anion response controlled-release membrane material for saline-alkali soil and preparation method thereof
Technical Field
The invention belongs to the technical field of soil improvement, and particularly relates to a special slow-release membrane material for an anion response saline-alkali soil and a preparation method thereof.
Background
Saline-alkali soil is in nearly hundreds of countries in five continents worldwideThe regions are distributed, and the incomplete statistics of UNESCO and FAO show that the global saline-alkali soil area is about 945 multiplied by 106hm2And the total area of saline-alkali soil in China is about 9.913 multiplied by 107hm2. Along with the growth of the advancing population of the society, the problems of land resource shortage and ecological environment deterioration are accompanied, the saline-alkali soil is used as an important land resource, the total area is large, the distribution is wide, according to the data, the area of the saline-alkali soil with agricultural utilization potential in China is about 2 hundred million mu, and nearly 80% of the saline-alkali soil in China is not reasonably developed and utilized, so that the scientific management, development and utilization of the saline-alkali soil resource have very important practical significance.
However, saline-alkali soil has high pH and large salt content, which seriously restricts the sustainable and stable production development of agriculture in China, and saline-alkali soil has the problems of low nutrient availability in soil, poor physical and chemical properties of soil and the like, which influence the growth and development of plants, so that the high yield and high efficiency of crops are realized on the saline-alkali soil, on one hand, the improvement of soil environment needs to be performed, and on the other hand, the combination of soil cultivation and land cultivation is performed in cooperation with nutrient supply required by the growth of the crops, so that the sustainable development of the saline-alkali soil production is realized.
There are many current methods for improving and utilizing saline and alkaline land, and the application of sustained/controlled release agricultural formulations is one of the effective measures. The slow/controlled release agricultural preparation greatly slows down the dissolution rate of nitrogen, phosphorus, potassium, modifying agent and the like through the slow release effect of the coating material, and reduces the salt damage superposition of the quick-acting preparation to seeds and seedlings. It has a great development space in the aspects of improving the utilization rate of agricultural preparations, saving cost, reducing environmental pollution and the like, and has become a research hotspot in the field.
The currently widely used coating materials comprise sulfonic acid and organic polymer materials, but the coating materials are brittle, poor in water resistance and short in slow release period, and the research on the coating materials specially aiming at saline-alkali soil is still in the starting stage, so that the research on the slow release film is heavy and far.
The total alkalinity of the soil is mainly related to the weak acid radical ion content in the soil, and depends on the difference of soil anions (such asHCO3 -、CO3 2-、SO4 2-、Cl-Etc.), the types of the saline-alkali soil mainly distributed in China comprise coastal saline-alkali soil rich in chloride, northwest flooded plain saline-alkali soil containing chloride and sulfate, northwest inland desert saline-alkali soil rich in sulfate, northeast grassland saline-alkali soil rich in carbonate/bicarbonate and the like. Different types of saline-alkali soil anion response materials are reasonably selected to serve as alkali-resistant monomers aiming at different types of saline-alkali soil, saline-alkali soil anions in the soil are passivated, and the sustained and controlled release performance of the membrane aiming at different saline-alkali soil is improved.
Disclosure of Invention
The invention aims to provide a special controlled-release membrane material for saline-alkali soil and a preparation method thereof.
The special controlled-release membrane material for saline-alkali soil provided by the invention is prepared from the following raw materials in parts by weight: 300-1000 parts of organic high polymer material, 300-2000 parts of organic solvent, 0.05-5 parts of catalyst, 0.05-2 parts of cross-linking agent, 0-20 parts of anion response material and 100-1000 parts of distilled water, wherein the endpoint value is 0, and the endpoint value is not required;
specifically, the special controlled-release membrane material for saline-alkali soil is prepared from the following raw materials in parts by weight: 300-1000 parts of organic polymer material, 300-1500 parts of organic solvent, 0.05-5 parts of catalyst, 0.05-2 parts of cross-linking agent, 10-20 parts of anion response material and 100-1000 parts of distilled water.
In the special controlled-release membrane material for saline-alkali soil, the organic polymer material comprises chitin and polyamino acid; wherein the mass ratio of the chitin to the polyamino acid can be 1-5: 1, specifically 1:1, 3:1, 2:1 or 5: 1;
the chitin can be any one or mixture of more of the following substances: n- (2-hydroxy-3-trimethylammonio chloride) propyl chitosan, carboxymethyl chitosan, amino chitin, hydroxyethyl chitin, deacetylated chitin, and carboxymethyl chitin;
the molecular weight of the chitin can be 50-100 kDa;
the polyamino acid can be polyglutamic acid and/or polyaspartic acid;
the polyamino acid may have a molecular weight of: 60-200 KDa;
the organic solvent may be a mixture of any one or more of: at least one of benzene, toluene, xylene, pentane, hexane, octane, cyclohexane, cyclohexanone, toluene cyclohexanone, chlorobenzene, dichlorobenzene, dichloromethane, methanol, ethanol, isopropanol, diethyl ether, propylene oxide, methyl acetate, ethyl acetate, propyl acetate, acetone, methyl butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol, ethanol, styrene, carbon tetrachloride and chloroform;
the catalyst may be a mixture of any one or more of: phosphoric acid, boric acid, sulfonic acid, methyl benzenesulfonic acid, sulfuric acid, tin sulfate, zirconium oxide, polymeric resin, cation exchange resin, heteropolytungstic acid, chromium sulfate;
the cross-linking agent may be a mixture of any one or more of: hydroxybenzoic acid, gluconic acid, 2-hydroxypropionic acid, glyceric acid, lactic acid, salicylic acid, citric acid, tartaric acid, gallic acid, acrylic resin, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and p-phenylene diisocyanate;
the anion response material is selected according to the types of the saline-alkali soil rich in anions:
for Cl-rich-The anion-responsive material comprises: 6, 8-difluoro-1- (2-fluoroethyl) 1, 4-dihydro-7- (4-methyl-1-piperazinyl) -4-oxo-3-quinolinecarboxylic acid;
for the enrichment of CO3 2-The anion-responsive material comprises: one or more of calcium gluconate, calcium hydrogen phosphate, calcium lactate, calcium chloride, calcium oxalate, calcium carbonate, calcium phosphate, calcium fluoride, calcium nitrate, calcium chlorate, calcium perchlorate, calcium bicarbonate, and calcium dihydrogen phosphate;
for HCO-rich3 -The anion-responsive material comprises: ferrous sulfate, ferrous nitrate, ferrous chromate, ferrous oxalate, siliconOne or more of ferrous acid and ferrous tartrate;
for rich SO4 2-The anion-responsive material comprises: one or more of barium nitrate, barium carbonate and barium chloride;
the special controlled-release membrane material for saline-alkali soil is prepared by the method comprising the following steps:
1) dissolving polyamino acid into an organic solvent to prepare a solution, and dispersing chitin into the solution to obtain an oil phase system a;
2) dissolving the anion response material in water to prepare a saturated solution, adding the saturated solution into the oil phase system a, and mixing to obtain a mixed phase b;
3) adding a cross-linking agent and a catalyst into the mixed phase b to form a homogeneous mixture c;
4) and (3) after the homogeneous mixture c reacts for a period of time, pouring the homogeneous mixture c onto a base material, drying, then washing with an alkali solution, and drying to obtain the special controlled release membrane material for the saline-alkali soil.
In the step 1) of the method, the ratio of the polyamino acid to the chitosan is 1-5: 1; by varying the amount and ratio of the two polymers, the binding sites for interaction with the responsive material can be varied;
in the step 2), aiming at the coastal saline-alkali soil rich in chloride, the anion response material is prepared by aiming at HCO3 -Of an anion-responsive material, for CO3 2-In response to SO4 2-And to Cl-The anion response materials comprise the following components in parts by mass: 0-1: 0-1: 0-1: 5-10 (specifically 1:0.3:0.5:10), wherein 0 is not preferred;
aiming at north China flooding plain saline-alkali land rich in chloride and sulfate, the anion response material is prepared by aiming at HCO3 -Of an anion-responsive material, for CO3 2-In response to SO4 2-And to Cl-The anion response materials comprise the following components in parts by mass: 0-1: 0-1: 5-10: 5-10 (specifically 0.5:1:8:8), wherein the endpoint value is 0 is not preferred;
for the northwest inland desert saline-alkali soil rich in sulfate, the anion response material is prepared by aiming at HCO3 -Of an anion-responsive material, for CO3 2-In response to SO4 2-And to Cl-The anion response materials comprise the following components in parts by mass: 0-1: 0-1: 5-10: 0-1 (specifically 0.5:0.5:10:0.5), wherein 0 is not preferable;
aiming at northeast prairie saline-alkali soil rich in carbonate/bicarbonate, the anion response material is prepared by aiming at HCO3 -Of an anion-responsive material, for CO3 2-In response to SO4 2-And to Cl-The anion response materials comprise the following components in parts by mass: 5-10: 5-10: 0-1: 0 to 1 (specifically 6: 6:0.5:0.5), wherein 0 is not preferable.
In the step 4) of the method, the reaction temperature can be 20-35 ℃, the reaction time can be 1-8 hours, and the substrate can be a polytetrafluoroethylene plate specifically;
the drying conditions may be: drying for 5-12 h at 20-70 ℃;
and drying at 50-70 ℃.
The application of the special controlled-release membrane material for saline-alkali soil in the preparation of the saline-alkali soil coated controlled-release agricultural preparation also belongs to the protection range of the invention.
In the application, the saline-alkali soil coated controlled-release agricultural preparation is a preparation with at least one of the following functions:
1) the total salt content and the pH value of the soil are reduced,
2) adjusting the pH value of the soil and controlling the release of nutrients,
3) improve the quality of crops.
The invention also provides a saline-alkali soil coated controlled-release agricultural preparation which is prepared by spraying or coating the special saline-alkali soil controlled-release membrane material on the surface of the core material of the agricultural preparation.
The mass ratio of the special controlled-release membrane material for the saline-alkali soil to the core material of the agricultural preparation can be 10-50: 500, specifically 10-200: 500. 20: 500. 10: 500 or 15: 500, a step of;
the core material of the agricultural preparation can be humic acid.
The invention adds two polymer materials with hydrogen bond interaction and anion response materials to develop the special controlled-release membrane material aiming at different types of saline-alkali soil. By varying the amount and ratio of the two polymers, the binding sites for interaction with the responsive material can be varied.
Compared with the prior sustained-release membrane material, the sustained-release membrane material special for the saline-alkali soil, which is obtained by modifying the biodegradable organic polymer, has the following obvious advantages:
1) the added anion response material is taken as alkali-resistant monomer and combined into the polymer system through hydrogen bond action, the adding proportion is changed, and the Cl which causes the alkalinity to be increased in different types of soil-、HCO3 -、CO3 2-、SO4 2-The ions are subjected to precipitation reaction, so that anions in the soil are passivated, the transmittance of materials in the membrane is slowed down, and meanwhile, the total salt content of the soil is reduced when the materials enter a plough layer along with irrigation water;
2) the main body of the invention is organic polymer, which can provide a large amount of carbon structures after being applied into soil, provide cementing substances for aggregates with small particle size and release nutrients;
3) the main organic polymer can promote the activity of microorganisms in soil, enhance the disease resistance of crops and improve the quality of the crops;
4) the used high polymer materials are degradable natural high polymer materials, so that the soil cannot be polluted, and the polyamino acid is degraded to generate ammonia gas, so that the pH value of the soil can be reduced by decomposing the ammonia gas.
Detailed Description
The present invention is described below with reference to specific embodiments, but the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified;
reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Weighing the components in a mass ratio of 1:1 part of hydroxyethyl chitin and 200 parts of polyaspartic acid, respectively dissolving the polyaspartic acid and the hydroxyethyl chitin in 500 parts of chloroform to prepare a substrate solution, adding 1 part of ferrous sulfate, 0.3 part of calcium gluconate, 0.5 part of barium nitrate and 10 parts of saturated solution of 6, 8-difluoro-1- (2-fluoroethyl) 1, 4-dihydro-7- (4-methyl-1-piperazinyl) -4-oxo-3-quinolinecarboxylic acid into the substrate solution, then 0.05 part of hydroxybenzoic acid and 0.05 part of sulfuric acid are added, evenly stirred to prepare the coating liquid, the reaction is carried out for 2 hours at the temperature of 20 ℃, finally the coating liquid is poured on an acrylic plate, then drying for 8h at room temperature, washing with ammonia water, and drying at 50 ℃ to obtain the required special slow-release coating material rich in chloride for the coastal saline-alkali soil.
Example 2
Weighing the components in a mass ratio of 3:1, 300 parts of carboxymethyl chitin and 100 parts of polyglutamic acid, respectively dissolving the polyglutamic acid and the carboxymethyl chitin into 800 parts of carbon tetrachloride to prepare a solution, adding 0.5 part of ferrous nitrate, 1 part of calcium phosphate, 8 parts of barium carbonate and 8 parts of saturated solution of 6, 8-difluoro-1- (2-fluoroethyl) 1, 4-dihydro-7- (4-methyl-1-piperazinyl) -4-oxo-3-quinolinecarboxylic acid into a substrate solution, then 0.05 part of gluconic acid and 0.08 part of phosphoric acid are added, evenly stirred to prepare coating liquid, the coating liquid reacts for 5 hours at the temperature of 26 ℃, finally the coating liquid is poured on an acrylic plate, then drying for 10h at room temperature, washing with ammonia water, and drying at 50 ℃ to obtain the required special controlled-release coating material containing chloride and sulfate for the North China flooding plain saline-alkali soil.
Example 3
Weighing the components in a mass ratio of 2:1 of chitin amino 400 and 200 of polyaspartic acid, dissolving the polyaspartic acid and the chitin amino in 1000 parts of ether to prepare solution, adding 0.5 part of ferrous oxalate, 0.5 part of calcium lactate, 10 parts of barium carbonate and 0.5 part of saturated solution of 6, 8-difluoro-1- (2-fluoroethyl) 1, 4-dihydro-7- (4-methyl-1-piperazinyl) -4-oxo-3-quinolinecarboxylic acid into the substrate solution, then adding 0.08 part of 2-hydroxypropionic acid and 0.08 part of boric acid, uniformly stirring to prepare a coating liquid, reacting for 8 hours at 32 ℃, finally pouring the coating liquid on an acrylic plate, then drying for 6h at room temperature, washing with ammonia water, and drying at 70 ℃ to obtain the special controlled-release coating material rich in sulfate for the northwest inland desert saline-alkali soil.
Example 4
Weighing the components in a mass ratio of 5:1 of deacetylated chitin and 100 of polyglutamic acid, respectively dissolving the polyglutamic acid and the deacetylated chitin into 1200 parts of cyclohexanone to prepare a solution, adding a saturated solution of 6 parts of ferrous silicate, 6 parts of calcium nitrate, 0.5 part of barium nitrate and 0.5 part of 6, 8-difluoro-1- (2-fluoroethyl) 1, 4-dihydro-7- (4-methyl-1-piperazinyl) -4-oxo-3-quinolinecarboxylic acid into a substrate solution, then adding 1.15 parts of glyceric acid and 1.55 parts of sulfonic acid, uniformly stirring to prepare a coating liquid, reacting for 6 hours at the temperature of 30 ℃, finally pouring the coating liquid on an acrylic plate, and then drying the mixture at room temperature for 10h, washing the mixture with ammonia water, and drying the mixture at 60 ℃ to obtain the required carbonate/bicarbonate-rich sustained and controlled release coating material special for the northeast grassland saline-alkali soil.
Example 5
The coated slow-release modifying agent prepared from the slow-release and controlled-release membrane material 4 is prepared by the following steps: uniformly spraying a sustained-release membrane material on the surface of humic acid, and drying at 40 ℃ to obtain a coated sustained-release modifier; wherein the mass ratio of the slow release membrane material to the humic acid is 20: 500.
100g of saline-alkali soil sample (belonging to northeast grassland saline-alkali soil rich in carbonate/bicarbonate) in white city of Jilin province, namely Tongshui county, with the pH value of 10.5, the conductivity EC of 2.99ds/m and the soil porosity of 31.8 percent is respectively weighed for indoor culture, water (100mL) is poured once a week after the coated slow-release modifier is applied to the soil, and the soil sample is subjected to measurement of various physicochemical properties after 3 months.
Through detection, the pH value of the soil is reduced to 9.4 after the slow release modifier is applied, which shows that the slow release modifier can relieve alkaline soil. The conductivity is reduced by 31.6 percent, the soil porosity is improved by 1.3 percent, and the initial release rate of the obtained coated slow-release modifying agent is 9.6 percent.
TABLE 1 Effect of sustained and controlled Release improvers on soil aggregates
Figure BDA0002771458510000061
After application of the slow release modifier, the number of large agglomerates (>0.25mm) increased significantly.
Example 6
The coated slow-release modifying agent prepared from the slow-release and controlled-release membrane material 1 is prepared by the following steps: uniformly spraying a sustained-release membrane material on the surface of humic acid, and drying at 70 ℃ to obtain a coated sustained-release modifier; wherein the mass ratio of the slow release membrane material to the humic acid is 20: 1000.
the coated controlled-release modifier is used for planting Tianjin coastal rice in 2019 and 5-2019 and 10 months. The tested soil parameters (belonging to the coastal saline-alkali soil rich in chloride) are as follows: pH of 10.3, conductivity EC of 4.17ds/m, soil porosity of 35.1%
Through detection, the pH of 0-20 cm soil is reduced by 1.1 unit, the conductivity is reduced by 21.3%, the soil porosity is improved by 0.9%, the initial release rate of the obtained coated slow-release modifying agent is 11.8%, the release period is 45 days, and the rice yield is improved by 40.5%.
Example 7
A coating slow-release modifying agent prepared from the slow-release and controlled-release membrane material 3 is prepared by uniformly spraying the slow-release and controlled-release membrane material on the surface of humic acid, and drying at 70 ℃ to obtain the coating slow-release modifying agent; wherein the mass ratio of the slow release membrane material to the humic acid is 30: 1000.
the coating slow-release modifier is used for planting medlar in Jingyuan county of Gansu Baiyin City 5-2019 9. The parameters of the tested soil (belonging to the northwest inland desert saline-alkali soil rich in sulfate) are as follows: the pH was 8.9, the conductivity EC was 2.67ds/m, and the soil porosity was 32.9%.
Through detection, the pH of 0-20 cm soil is reduced by 0.8 unit, the conductivity is reduced by 18.3%, the soil porosity is improved by 1.1%, the initial release rate of the obtained coated slow-release modifying agent is 12.3%, the release period is 52 days, and the output of the medlar is improved by 42.5%.
Example 8
A coating slow-release modifying agent prepared from the slow-release and controlled-release membrane material 2 is prepared by uniformly spraying the slow-release and controlled-release membrane material on the surface of humic acid, and drying at 60 ℃ to obtain the coating slow-release modifying agent; wherein the mass ratio of the slow release membrane material to the humic acid is 20: 1000.
the coating slow-release modifier is used for planting potatoes in Tengzhou city in Shandong province in 5-2019 and 10-2019 in 2019. The parameters of the tested soil (belonging to north China flooding plain saline-alkali soil rich in chloride and sulfate) are as follows: the pH was 8.5, the conductivity EC was 3.13ds/m, and the soil porosity was 34.2%.
Through detection, the pH of 0-20 cm soil is reduced by 0.6 bit, the conductivity is reduced by 23.5%, the soil porosity is improved by 3.1%, the initial release rate of the obtained coated slow-release modifying agent is 17.4%, the release period is 59 days, and the potato yield is improved by 44.1%.

Claims (10)

1. A special controlled release membrane material for saline-alkali soil is prepared from the following raw materials in parts by weight: 300-1000 parts of organic high polymer material, 300-2000 parts of organic solvent, 0.05-5 parts of catalyst, 0.05-2 parts of cross-linking agent, 0-20 parts of anion response material and 100-1000 parts of distilled water, wherein the endpoint value is 0, and the method is not preferable.
2. The special controlled-release membrane material for saline-alkali soil according to claim 1, which is characterized in that: the organic polymer material comprises chitin and polyamino acid; wherein the mass ratio of the chitin to the polyamino acid is 1-5: 1;
the chitin is a mixture of any one or more of the following components: n- (2-hydroxy-3-trimethylammonio) propyl chitosan, carboxymethyl chitosan, amino chitin, hydroxyethyl chitin, deacetylated chitin, carboxymethyl chitin;
the molecular weight of the chitin is 50-100 kDa;
the polyamino acid is polyglutamic acid and/or polyaspartic acid;
the molecular weight of the polyamino acid is as follows: 60-200 KDa.
3. The special controlled-release membrane material for saline-alkali soil according to claim 1 or 2, characterized in that: the organic solvent is a mixture of any one or more of the following: at least one of benzene, toluene, xylene, pentane, hexane, octane, cyclohexane, cyclohexanone, toluene cyclohexanone, chlorobenzene, dichlorobenzene, dichloromethane, methanol, ethanol, isopropanol, diethyl ether, propylene oxide, methyl acetate, ethyl acetate, propyl acetate, acetone, methyl butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol, ethanol, styrene, carbon tetrachloride and chloroform;
the catalyst is a mixture of any one or more of the following: phosphoric acid, boric acid, sulfonic acid, methyl benzenesulfonic acid, sulfuric acid, tin sulfate, zirconium oxide, polymeric resin, cation exchange resin, heteropolytungstic acid, chromium sulfate;
the cross-linking agent is any one or a mixture of more of the following: hydroxybenzoic acid, gluconic acid, 2-hydroxypropionic acid, glyceric acid, lactic acid, salicylic acid, citric acid, tartaric acid, gallic acid, acrylic resin, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and p-phenylene diisocyanate.
4. The special controlled-release membrane material for saline-alkali soil as claimed in any one of claims 1 to 3, wherein: for Cl-rich-The anion-responsive material comprises: 6, 8-difluoro-1- (2-fluoroethyl) 1, 4-dihydro-7- (4-methyl-1-piperazinyl) -4-oxo-3-quinolinecarboxylic acid;
for the enrichment of CO3 2-The said anion in the saline-alkali soilThe sub-response materials include: one or more of calcium gluconate, calcium hydrogen phosphate, calcium lactate, calcium chloride, calcium oxalate, calcium carbonate, calcium phosphate, calcium fluoride, calcium nitrate, calcium chlorate, calcium perchlorate, calcium bicarbonate, and calcium dihydrogen phosphate;
for HCO-rich3 -The anion-responsive material comprises: one or more of ferrous sulfate, ferrous nitrate, ferrous chromate, ferrous oxalate, ferrous silicate and ferrous tartrate;
for rich SO4 2-The anion-responsive material comprises: one or more of barium nitrate, barium carbonate and barium chloride.
5. The method for preparing the special controlled-release membrane material for the saline-alkali soil, which is disclosed by any one of claims 1 to 4, comprises the following steps of:
1) dissolving polyamino acid into an organic solvent to prepare a solution, and dispersing chitin into the solution to obtain an oil phase system a;
2) dissolving the anion response material in water to prepare a saturated solution, adding the saturated solution into the oil phase system a, and mixing to obtain a mixed phase b;
3) adding a cross-linking agent and a catalyst into the mixed phase b to form a homogeneous mixture c;
4) and (3) after the homogeneous mixture c reacts for a period of time, pouring the homogeneous mixture c onto a base material, drying, then washing with an alkali solution, and drying to obtain the special controlled release membrane material for the saline-alkali soil.
6. The method of claim 5, wherein: in the step 2), aiming at the coastal saline-alkali soil rich in chloride, the anion response material is prepared by aiming at HCO3 -Of an anion-responsive material, for CO3 2-In response to SO4 2-And to Cl-The anion response materials comprise the following components in parts by mass: 0-1: 0-1: 0-1: 5-10, wherein the endpoint value is 0 is not preferred;
aiming at north China flooding plain saline-alkali soil containing chloride and sulfate, the anion response material is prepared by aiming at HCO3 -Of an anion-responsive material, for CO3 2-In response to SO4 2-And to Cl-The anion response materials comprise the following components in parts by mass: 0-1: 0-1: 5-10: 5-10, wherein the endpoint value is 0 is not preferred;
for the northwest inland desert saline-alkali soil rich in sulfate, the anion response material is prepared by aiming at HCO3 -Of an anion-responsive material, for CO3 2-In response to SO4 2-And to Cl-The anion response materials comprise the following components in parts by mass: 0-1: 0-1: 5-10: 0 to 1, wherein the endpoint value is 0 is not preferable;
aiming at northeast prairie saline-alkali soil rich in carbonate/bicarbonate, the anion response material is prepared by aiming at HCO3 -Of an anion-responsive material, for CO3 2-In response to SO4 2-And to Cl-The anion response materials comprise the following components in parts by mass: 5-10: 5-10: 0-1: 0 to 1, wherein 0 is not preferable.
7. The method according to claim 5 or 6, characterized in that: in the step 4), the reaction temperature is 20-35 ℃, and the reaction time is 1-8 h;
the drying conditions are as follows: drying for 5-12 h at 20-70 ℃;
and drying at 50-70 ℃.
8. The application of the special controlled-release membrane material for saline-alkali soil in the preparation of saline-alkali soil coated controlled-release agricultural preparations according to any one of claims 1 to 4, wherein the saline-alkali soil coated controlled-release agricultural preparations are preparations with at least one function of the following functions:
1) the total salt content and the pH value of the soil are reduced,
2) adjusting the pH value of the soil and controlling the release of nutrients,
3) improve the quality of crops.
9. A saline-alkali soil coated controlled-release agricultural preparation, which is prepared by spraying or coating the special saline-alkali soil controlled-release membrane material of any one of claims 1 to 4 on the surface of a core material of the agricultural preparation.
10. The controlled release agricultural formulation of a salt-alkaline earth coated film according to claim 9, characterized in that: the mass ratio of the special controlled-release membrane material for the saline-alkali soil to the core material of the agricultural preparation is 10-50: 500, a step of;
the core material of the agricultural preparation is humic acid.
CN202011250614.7A 2020-11-11 2020-11-11 Special anion response controlled-release membrane material for saline-alkali soil and preparation method thereof Pending CN112279729A (en)

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CN104447027A (en) * 2014-12-12 2015-03-25 华南农业大学 Preparation method of in-situ reaction film-forming and hole-forming type controlled-release fertilizers
CN105131962A (en) * 2015-07-30 2015-12-09 中国农业大学 Saline land improver and preparation method thereof
CN107011058A (en) * 2017-05-09 2017-08-04 中国农业大学 A kind of anti-salt type function coating slowly/controlled releasing fertilizer and preparation method thereof
CN109777430A (en) * 2019-03-14 2019-05-21 中国农业大学 A kind of pH released microcapsule type macromolecule saline-alkali soil modifying agent and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104130056A (en) * 2014-07-18 2014-11-05 成都新柯力化工科技有限公司 pH-sensitive coated slow-release phosphate fertilizer and preparation method thereof
CN104447027A (en) * 2014-12-12 2015-03-25 华南农业大学 Preparation method of in-situ reaction film-forming and hole-forming type controlled-release fertilizers
CN105131962A (en) * 2015-07-30 2015-12-09 中国农业大学 Saline land improver and preparation method thereof
CN107011058A (en) * 2017-05-09 2017-08-04 中国农业大学 A kind of anti-salt type function coating slowly/controlled releasing fertilizer and preparation method thereof
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Application publication date: 20210129