Plant anti-freezing solution composition as well as preparation method and application thereof

Abstract

The invention relates to a plant anti-freezing solution composition as well as a preparation method and application thereof. The composition comprises a film-forming agent, a film-forming initiator, a phosphorus-potassium fertilizer, an anti-freezing solution and the balance of water. The film-forming agent is polyvinyl alcohol and sodium alginate; the film forming initiator is at least one of potassium persulfate, azodiisobutyronitrile and cumene hydroperoxide; the phosphorus-potassium fertilizer is at least one of potassium phosphite and monopotassium phosphate; the anti-freezing liquid is at least one of ethylene glycol, alpha-propylene glycol and glycerol. The composition further contains a biostimulant, a biological bactericide, a plant growth regulator and a biological surfactant. The invention provides a preparation method of an anti-freezing solution composition and application of the anti-freezing solution composition to field crops, fruit trees, vegetables and gardens needing to be subjected to anti-freezing.

Description

Technical Field

[0001] This invention relates to the field of agricultural technology, specifically to a plant antifreeze composition and its preparation method. Background Technology

[0002] Low-temperature freezing damage severely threatens the survival and development of plants throughout their growth process. Whether it's the harsh winters of the north or the occasional cold snaps of spring in the south, both can cause irreparable damage to crops, flowers, fruit trees, and other plants. According to statistics, the annual agricultural economic losses due to low-temperature freezing damage reach billions of yuan. For example, in citrus-growing areas, once winter temperatures drop, the quality and yield of citrus fruits decline significantly. The fruit peel develops frostbite spots, the taste deteriorates, and sometimes the entire citrus tree dies from frost damage, causing a heavy economic blow to fruit farmers. In the flower industry, low-temperature freezing damage causes flowers to become deformed and wither, and leaves to turn yellow and wilt, severely affecting the ornamental value and marketability of the flowers.

[0003] The impact of frost damage on crops is mainly caused by ice formation in the intercellular spaces and within the cells. When the temperature drops rapidly, water in the intercellular spaces freezes first, and water vapor from surrounding cells condenses into the ice crystals, increasing their size and causing mechanical damage to the cell protoplasm. When the temperature drops rapidly below 0°C, in addition to freezing in the intercellular spaces, the protoplasm within the cells also freezes. These ice crystals severely damage the structure of biomembranes and organelles, disrupting the isolation of cell substructures and causing excessive dehydration of the cell protoplasm. This series of problems leads to the leakage of electrolytes from the cells, disrupting normal cellular metabolic functions. Simultaneously, low temperatures inhibit the activity of various enzymes in plants, hindering important physiological processes such as photosynthesis and respiration, thus affecting plant growth and development.

[0004] Therefore, a plant antifreeze composition and its preparation method are proposed. This composition regulates the absorption and utilization of phosphorus and potassium fertilizers through biostimulants, induces plant maturation through plant growth regulators, inhibits fungal reproduction through biological fungicides, isolates plants from low temperature erosion through one-way biofilms, and lowers the freezing point of plants through antifreeze, thus achieving the effect of heat preservation and frost resistance, and is also environmentally friendly and safe.

[0005] Currently, various protective measures have been adopted in agricultural production to combat the damage caused by freezing temperatures. Physical protection methods, such as covering with insulating materials, can provide some insulation, but they are cumbersome to implement, costly, and have limited effectiveness. Chemical antifreeze agents are widely used; however, some traditional chemical antifreeze agents contain environmentally harmful chemicals. Long-term use can pollute soil and water sources and may leave residues in agricultural products, posing a health risk. Furthermore, the antifreeze effect of some chemical antifreeze agents is greatly affected by environmental factors, and their protective capabilities are significantly reduced under extreme low-temperature conditions. While biological antifreeze products have environmental advantages, they often suffer from unstable active ingredients and short-lasting effects, making them difficult to meet the needs of actual agricultural production. Summary of the Invention

[0006] The purpose of this invention is to provide a plant antifreeze composition, its preparation method, and its application. This composition can effectively inhibit the formation and reproduction of ice nuclei, enhance and activate the activity of biological enzymes, accelerate the lignification process of plants, reduce and mitigate the damage of low temperatures to biofilms, and lower the freezing point value of plant cell membranes. Crops treated with the antifreeze effectively prevent leaves, flowers, and buds from freezing damage and enhance their resistance to low-temperature injury.

[0007] The objective of this invention is achieved through the following technical solution: This invention is a plant antifreeze composition. First, a film-forming agent is prepared using a biofilm-forming substance and an initiator. Then, phosphorus and potassium fertilizer and antifreeze are added to form a plant antifreeze composition. Further, biostimulants, biofungicides, plant growth regulators, and surfactants are added to formulate the antifreeze composition.

[0008] The inventors have discovered that a film-forming agent formed from sodium alginate and polyvinyl alcohol, when applied to the surface of plants, has an antifreeze effect. Simultaneously, potassium fertilizer also contributes to antifreeze properties. This invention utilizes sodium alginate and polyvinyl alcohol to polymerize into a film in the presence of an initiator; the phosphorus and potassium fertilizers possess both antifreeze properties and fertilizer effects; combined with diols, components of the antifreeze solution, to form a plant antifreeze composition.

[0009] The antifreeze contains diols, which act as solvents to dissolve some brassinolide plant growth regulators that are not easily soluble in water; biostimulants are added to the water-based components, and the final product is adjusted with surfactants to obtain the final antifreeze.

[0010] The antifreeze composition of the present invention further contains a bio-fungicide, wherein lactic acid can act as a bio-fungicide to prevent and control plant diseases. Potassium lactate is preferred as the bio-fungicide, as it can perform bactericidal effects while the potassium salt also has antifreeze properties.

[0011] Specifically, the plant-based antifreeze composition of the present invention comprises

[0012]

[0013] The film-forming agent is polyvinyl alcohol and sodium alginate, with a total content of 1-5%; the film-forming initiator is at least one of potassium persulfate, azobisisobutyronitrile, and cumene hydrogen peroxide, with a content of 0.3-1.5%; the phosphorus and potassium fertilizer is at least one of potassium phosphite and potassium dihydrogen phosphate, with a content of 5-15%; the antifreeze is at least one of ethylene glycol, α-propylene glycol, and glycerol, with a content of 1-5%.

[0014] The plant-based antifreeze composition of the present invention further contains biostimulants. The composition comprises:

[0015]

[0016] The biostimulant is composed of mineral-derived potassium humate, fish protein, and chitosan, a chitin derivative, with the following content: potassium humate 1-10%; fish protein 1-3%; and chitosan 1-2%. The biostimulant also includes amino acids, specifically two or more of valine, polyglutamic acid, tryptophan, and serine. Its total content is 1-3%.

[0017] The plant-based antifreeze composition of this invention further contains a bio-fungicide. It comprises...

[0018]

[0019] The biocidal agent is lactic acid and its salts, preferably potassium lactate. Its content is 1-5%.

[0020] The plant antifreeze composition of the present invention further contains a plant growth regulator. It comprises:

[0021]

[0022] The plant growth regulators are 14-hydroxybrassinolide and tetramethylglutaric acid; their contents are 0.0075-0.01% for 14-hydroxybrassinolide and 1-2% for tetramethylglutaric acid.

[0023] The plant-based antifreeze composition of the present invention further contains a biosurfactant. It comprises...

[0024]

[0025] The specific biosurfactant is glutamic acid betaine, with a content of 1-8%.

[0026] The preferred plant-based antifreeze composition of the invention contains,

[0027]

[0028]

[0029] The film-forming agent is polyvinyl alcohol alginate / sodium, with a content of 1-5%; it is polymerized by at least one of potassium persulfate, azobisisobutyronitrile, and cumene hydrogen peroxide, with a film-forming initiator content of 0.3-1.5%; the phosphorus and potassium fertilizer is at least one of potassium phosphite and potassium dihydrogen phosphate, with a content of 5-15%; the antifreeze is at least one of ethylene glycol, α-propylene glycol, and glycerol, with a content of 1-5%; the biostimulant is composed of mineral-derived potassium humate, fish protein, and chitosan, a chitin derivative, with contents of: mineral-derived potassium humate 1-10%, fish protein 1-3%, and chitosan, respectively. The product contains 1-2% chitosan derivatives; biostimulants also include amino acids, specifically two or more combinations of valine, polyglutamic acid, tryptophan, and serine, with a total content of 1-3%; a biofungicide, specifically lactic acid and its salts, preferably potassium lactate, with a content of 1-5%; a plant growth regulator, specifically 14-hydroxybrassinolide and tetramethylglutaric acid, with contents of 0.0075-0.01% for 14-hydroxybrassinolide and 1-2.01% for tetramethylglutaric acid; and a biosurfactant, specifically betaine glutamate, with a content of 1-8%.

[0030] The plant-based antifreeze composition of the present invention comprises the following components by weight percentage:

[0031] The biofilm-forming agent is prepared by adding 1-5% polyvinyl alcohol and sodium alginate, 0.3-1.5% potassium persulfate, 5-15% potassium phosphite, 1-5% antifreeze, 1-15% mineral-derived fulvic acid, 1-5% fish protein, 1-2% chitosan (a chitin derivative), 1-10% amino acids, 1-5% potassium lactate, 0.0075-0.01% 14-hydroxybrassinolide, 1-2% tetramethylglutaric acid, 1-8% betaine glutamate, and water to make up to 100%.

[0032] The preferred technical solution of the present invention is that the antifreeze composition is prepared by using the biofilm-forming agent polyvinyl alcohol and sodium alginate 2-4%, potassium persulfate 0.5-1.0%, potassium phosphite 8-12%, antifreeze 2-4%, mineral humic acid 1-10%, fish protein 1-3%, chitosan (a chitin derivative) 1%, amino acids 1-8%, potassium lactate 1-4%, 14-hydroxybrassinolide 0.01%, tetramethylglutaric acid 1%, betaine glutamate 1-5%, and water to make up to 100%.

[0033] This invention also provides a method for preparing a plant antifreeze composition. In this invention, a biofilm-forming agent is first prepared. Then, based on the solubility of the various components added to the composition, polar substances are dissolved in water, and non-polar substances are dissolved in antifreeze diols to prepare aqueous solutions and antifreeze solutions respectively. The aqueous solutions and antifreeze solutions are then mixed, and if necessary, biosurfactants are added for emulsification to form a transparent liquid. The solution containing the dissolved active substances is then mixed with the film-forming agent to prepare the plant antifreeze fertilizer.

[0034] This invention further proposes a method for preparing a plant antifreeze composition. S1: First, polyvinyl alcohol is mixed with alginate / sodium to prepare a biofilm-forming agent in the presence of a film-forming initiator. S2: A polar component is dissolved in water to prepare its aqueous solution. The polar component includes: phosphorus and potassium fertilizer, biostimulant, and biofungicide. S3: An antifreeze solution or an antifreeze solution containing a plant growth regulator is mixed with the aqueous solution from S2 to form a solution. For the above mixed solution, a biosurfactant may be added to emulsify the solution if necessary. S4: The biofilm-forming agent prepared in step S1 is added to the mixed solution obtained in S3 to prepare the antifreeze composition.

[0035] In step S2, for an antifreeze composition containing phosphorus and potassium fertilizer, biostimulants and / or biocide, an aqueous solution containing phosphorus and potassium fertilizer, biostimulants and / or biocide can be prepared.

[0036] In step S3, for compositions containing plant growth regulators, 14-hydroxybrassinolide and tetramethylglutaric acid can be dissolved in antifreeze, added to the solution in S2 and stirred, and finally emulsified with glutamic acid betaine.

[0037] Furthermore, whether or not to use a biosurfactant for emulsification in step S3 depends on the types and amounts of the components added to the antifreeze composition. When adding a small amount of a component can form an aqueous solution and a clear aqueous solution of the antifreeze, emulsification with a surfactant is not necessary. When multiple antifreeze components are added, and the content of each component is high (i.e., to prepare a high-concentration antifreeze), a biosurfactant needs to be added to improve the solubility of the antifreeze composition.

[0038] The specific preparation method includes the following steps:

[0039] S1. Preparation of biofilm-forming agent: According to the ratio, first add polyvinyl alcohol and alginate / sodium to water, start stirring and heat, and control the temperature at 70-80℃ to form a mixed solution. Then add the initiator to polymerize polyvinyl alcohol and alginate / sodium to form a biofilm-forming agent A, and cool it for later use.

[0040] S2. Chelation of macronutrient fertilizers: Prepare an aqueous solution of phosphorus and potassium fertilizer to obtain substance B, and cool it for later use.

[0041] S3. Add the antifreeze to the substance B solution in S2 and stir to form a mixed solution.

[0042] S4. Add the biofilm-forming agent A prepared in step S1 to the mixed solution in S3, and after sufficient shearing, the plant antifreeze composition is obtained.

[0043] The preferred plant-based antifreeze composition of the present invention is prepared by the following steps:

[0044] S1. Preparation of biofilm-forming agent: According to the ratio, first add polyvinyl alcohol and alginic acid to water, start stirring and heat, and control the temperature at 70-80℃ to form a mixed solution. Then add potassium persulfate as an initiator to polymerize polyvinyl alcohol and alginic acid to form a biofilm-forming agent A. Cool and set aside for later use.

[0045] S2. Chelation of macro-element fertilizers: Add biostimulant mineral-derived potassium humate, amino acids, fish protein peptides, and chitosan, a chitin derivative, to a measured amount of water and stir thoroughly to dissolve. After heating and dissolving, add potassium phosphite and potassium lactate and carry out a chelation reaction at 70-80℃ for 1 hour to obtain substance B, which is then cooled for later use.

[0046] S3. Dissolve 14-hydroxybrassinolide and tetramethylglutaric acid in antifreeze, add chelate B from S2 and stir to mix, and finally add glutamic acid betaine for emulsification.

[0047] S4. After emulsification, add biofilm-forming agent A, and after sufficient shearing, the plant antifreeze composition is obtained.

[0048] This invention also provides uses of the above-described plant antifreeze composition, and uses of the composition prepared using the method of this invention. The above-described composition can be used in plant antifreeze and frost protection, wherein the plants include field crops, fruit trees, vegetables, and garden plants requiring frost protection.

[0049] The composition is applied by spraying the composition solution.

[0050] When used as a spray, apply at temperatures between -10°C and 5°C, once every 7 to 15 days, for 1 to 3 consecutive applications. Different concentrations of the antifreeze composition of this invention can be used depending on the level of temperature drop and the expected degree of frost damage. Higher concentrations of antifreeze provide superior antifreeze effects. Generally, a 100 to 4000 times, preferably 500 to 1000 times, dilution of the composition can be sprayed.

[0051] This invention relates to a plant antifreeze composition. This composition regulates the absorption and utilization of phosphorus and potassium fertilizers through biostimulants, improves the stability of plant cell membranes, accelerates the lignification process, induces plant maturation with plant growth regulators, reduces and mitigates the damage of low temperatures to biofilms, inhibits fungal growth with bio-fungicides, isolates plants from the erosion of low temperatures with a one-way biofilm, and lowers the freezing point within the plant, thus achieving a heat preservation and frost resistance effect. It effectively prevents frost damage to leaves, flowers, and buds, enhances resistance to low-temperature injury, and is environmentally friendly and safe. It can be used on all vegetables, crops, flowers, bonsai, and other perennial plants in most parts of my country, enhancing their water retention and cold resistance, alleviating and rehabilitating plants with mild to moderate frost damage, and improving crop yield and quality. Detailed Implementation

[0052] Preparation Example 1

[0053] The composition of this embodiment includes a film-forming agent, a film-forming initiator, a phosphorus and potassium fertilizer, an antifreeze, and water.

[0054]

[0055]

[0056] Material preparation

[0057] Film-forming agent preparation: First, add 150g of polyvinyl alcohol and 150g of sodium alginate to 620g of water, start stirring and heat, and control the temperature at 70-80℃ to form a mixed solution. Then add 80g of potassium persulfate initiator to polymerize polyvinyl alcohol and alginate to form a cross-linked gel-like biofilm-forming agent with a content of 30%.

[0058] Phosphorus and potassium fertilizer: potassium dihydrogen phosphate or potassium phosphite, with phosphorus content ≥52% and potassium content ≥34% to ensure the nutritional supply effect of the product.

[0059] Antifreeze: One or any two of ethylene glycol, α-propanediol, and glycerol, in a 1:1 ratio.

[0060] Water: Deionized water or purified water to avoid impurities in the water affecting product performance.

[0061] Preparation steps

[0062] In a clean and sufficiently large container, first add 600 grams of water. Slowly pour 100 grams of potassium phosphite into the water while stirring at medium speed for about 5 minutes to ensure the potassium phosphite is fully dissolved and the solution is homogeneous. Next, add 50 grams of ethylene glycol to the container and continue stirring, increasing the stirring speed to medium-high for about 10 minutes to ensure the potassium phosphite is evenly dissolved and to prevent precipitation or clumping. Finally, add 100 grams of film-forming agent and bring the total volume to 1 kg with 150 grams of water. Stir at low speed for about 5 minutes to fully disperse the film-forming agent and mix it thoroughly with the solution to form a stable system. After stirring, visually inspect the prepared product to ensure there is no obvious precipitation, stratification, or impurities. If necessary, filter the product using a filtration device to remove any possible small particulate impurities.

[0063] Preparation Example 2

[0064] The plant-based antifreeze composition of this embodiment further contains biostimulants.

[0065] Material preparation

[0066] The film-forming agent was prepared using the same method as in Example 1.

[0067] Biostimulants: Biostimulants are composed of mineral-derived potassium humate, fish protein, and chitosan, a chitin derivative, with the following content: 5% mineral-derived potassium humate; 2% fish protein; and 1.5% chitosan. The biostimulant also includes amino acids, specifically two or more of valine, polyglutamic acid, tryptophan, and serine. Their total content is 1.5%.

[0068] Preparation steps

[0069] In a clean and sufficiently large container, first add 500g of water. Slowly pour 100g of potassium dihydrogen phosphate into the water while stirring at medium speed for about 5 minutes to ensure the potassium dihydrogen phosphate is fully dissolved and homogeneous. Next, add 50g of mineral-derived potassium humate, 20g of fish protein, 15g of chitosan, and 15g of mixed amino acids (5g each of valine, polyglutamic acid, and tryptophan). Heat to dissolve and chelate the phosphorus and potassium elements for at least 60 minutes. After chelation, add 50g of ethylene glycol and continue stirring, increasing the stirring speed to medium-high for about 10 minutes to form a brownish-brown homogeneous solution. Finally, add 100g of film-forming agent and bring the total volume to 1kg with 150g of water. Stir at low speed for about 5 minutes to fully disperse the film-forming agent and mix it thoroughly with the solution to form a stable system. After stirring, inspect the prepared product for appearance to ensure there is no obvious precipitation, stratification, or impurities. If necessary, filtration equipment can be used to filter the product to remove any small particulate impurities that may be present.

[0070] Preparation Example 3

[0071] The plant-based antifreeze composition of this embodiment further contains a biocide.

[0072] Material preparation

[0073] The film-forming agent was prepared using the same method as in Example 1.

[0074] Biocides: Salts formed from lactic acid, with potassium salts exhibiting the highest activity; potassium lactate is preferred.

[0075] Preparation steps

[0076] In a clean and sufficiently large container, first add 500g of water. Slowly pour in 100g of potassium phosphite and 30g of potassium lactate while stirring at medium speed to ensure the potassium phosphite and potassium lactate are fully dissolved in the water for about 5 minutes, ensuring a homogeneous solution. Next, add 50g of mineral-derived potassium humate, 20g of fish protein, 15g of chitosan, and 15g of mixed amino acids (5g of valine and 10g of polyglutamic acid). Heat to dissolve and chelate the phosphorus and potassium elements for at least 60 minutes. After chelation, add 50g of α-propanediol and continue stirring, increasing the stirring speed to medium-high for about 10 minutes to form a brownish-brown homogeneous solution. Finally, add 100g of film-forming agent and bring the total volume to 1kg with 120g of water. Stir at low speed for about 5 minutes to completely disperse the film-forming agent and thoroughly mix it with the solution to form a stable system. After stirring, inspect the prepared product for appearance to ensure there is no obvious precipitation, stratification, or impurities. If necessary, filtration equipment can be used to filter the product to remove any small particulate impurities that may be present.

[0077] Preparation Example 4

[0078] The plant antifreeze composition of this embodiment further contains a plant growth regulator.

[0079]

[0080]

[0081] Material preparation

[0082] The film-forming agent was prepared using the same method as in Example 1.

[0083] Plant growth regulators: 0.0075-0.01% 14-hydroxybrassinolide and 1-2% tetramethylglutaric acid. Since 14-hydroxybrassinolide has the highest activity among brassinolide products, it can enhance the crop's stress resistance when combined with tetramethylglutaric acid. After formula screening, the final dosage of 14-hydroxybrassinolide was determined to be 0.01%, and the dosage of tetramethylglutaric acid was determined to be 1%.

[0084] Preparation steps

[0085] In a clean and sufficiently large container, first add 500 grams of water. Slowly pour 100 grams of potassium dihydrogen phosphate and 30 grams of potassium lactate into the water while stirring at medium speed with a stirrer to fully dissolve the potassium dihydrogen phosphate and potassium lactate in the water. Stir for about 5 minutes to ensure the solution is homogeneous. Next, add 50g of potassium humate (mineral-derived), 20g of fish protein, 15g of chitosan, and 15g of mixed amino acids (4g valine, 4g polyglutamic acid, 4g tryptophan, and 3g serine). Heat to dissolve and chelate phosphorus and potassium elements for 60 minutes. Dissolve 0.1g of 14-hydroxybrassinolide and 10g of tetramethylglutaric acid in 50g of antifreeze (25g ethylene glycol and 25g propylene glycol), then add to the chelated solution and continue stirring. The stirring speed can be appropriately increased to medium-high speed for about 10 minutes to form a brownish-brown homogeneous solution. Finally, add 100g of film-forming agent and make up to 109.9g of water to 1kg. Stir at low speed for about 5 minutes to completely disperse the film-forming agent and fully mix it with the solution to form a stable system. After stirring, inspect the prepared product for appearance to ensure there is no obvious precipitation, stratification, or impurities. If necessary, use a filtration device to filter the product to remove any possible small particulate impurities.

[0086] Preparation Example 5

[0087] The most preferred embodiment of the plant antifreeze composition of the present invention is a composition containing a biostimulant, a biofungicide, a plant growth regulator, and a biosurfactant.

[0088] Material preparation

[0089] Film-forming agent preparation: First, add 150g of polyvinyl alcohol and 150g of alginic acid to 620g of water, start stirring and heat, and control the temperature at 70-80℃ to form a mixed solution. Then add 80g of potassium persulfate initiator to polymerize polyvinyl alcohol and alginic acid to form a cross-linked gel-like biofilm-forming agent with a content of 30%.

[0090] Phosphorus and potassium fertilizer: potassium dihydrogen phosphate or potassium phosphite, with phosphorus content ≥52% and potassium content ≥34% to ensure the nutritional supply effect of the product.

[0091] Antifreeze: One or any two of ethylene glycol, α-propanediol, and glycerol, in a 1:1 ratio.

[0092] Biostimulants: Biostimulants are composed of mineral-derived potassium humate, fish protein, and chitosan, a chitin derivative, with the following content: 5% mineral-derived potassium humate; 2% fish protein; and 1.5% chitosan. The biostimulant also includes amino acids, specifically two or more of valine, polyglutamic acid, tryptophan, and serine. Their total content is 1.5%.

[0093] Biocides: Salts formed from lactic acid, with potassium salts exhibiting the highest activity; potassium lactate is preferred.

[0094] Plant growth regulators: 0.0075-0.01% 14-hydroxybrassinolide and 1-2% tetramethylglutaric acid. Since 14-hydroxybrassinolide has the highest activity among brassinolide products, it can enhance the crop's stress resistance when combined with tetramethylglutaric acid. After formula screening, the final dosage of 14-hydroxybrassinolide was determined to be 0.01%, and the dosage of tetramethylglutaric acid was determined to be 1%.

[0095] Surfactants: Surfactants play a stabilizing role in this system, preventing stratification, water separation, and oil separation during long-term storage. The preferred bioactive agent in this formulation is glutamic acid betaine, added at a dosage of 4%.

[0096] Water: Deionized water or purified water to avoid impurities in the water affecting product performance.

[0097] Preparation steps

[0098] In a clean and sufficiently large container, first add 500 grams of water. Then, slowly pour 100 grams of potassium phosphite and 30 grams of potassium lactate into the water while stirring at medium speed to ensure that the potassium phosphite and potassium lactate are fully dissolved in the water. Stir for about 5 minutes to ensure that the solution is homogeneous. Next, add 50g of potassium humate (mineral-derived), 20g of fish protein, 15g of chitosan, and 15g of mixed amino acids (4g valine, 4g polyglutamic acid, 4g tryptophan, and 3g serine). Heat to dissolve and chelate phosphorus and potassium elements for 60 minutes. Dissolve 0.1g of 14-hydroxybrassinolide and 10g of tetramethylglutaric acid in 50g of antifreeze (25g ethylene glycol and 25g glycerol), then add to the chelated solution and continue stirring. The stirring speed can be appropriately increased to medium-high speed for about 10 minutes to form a brownish-brown homogeneous solution. Finally, add 100g of film-forming agent and 40g of glutamic acid betaine, and add 69.9g of water to a total volume of 1kg. Stir at low speed for about 5 minutes to completely disperse the film-forming agent and thoroughly mix it with the solution to form a stable system. After stirring, inspect the prepared product for appearance to ensure there is no obvious precipitation, stratification, or impurities. If necessary, filtration equipment can be used to filter the product to remove any small particulate impurities that may be present.

[0099] Examples of antifreeze effects

[0100] Example 1 of efficacy

[0101] I. Experimental Objective

[0102] To investigate the protective effects of crop antifreeze agents of different embodiments on crops in low-temperature environments, compare the advantages and disadvantages of each embodiment, and screen out the antifreeze agent embodiment with the best effect, so as to provide a scientific basis for crop frost protection in agricultural production.

[0103] II. Test Materials

[0104] Crop variety: Select winter wheat seedlings that are growing well and are uniform, with a seedling age of about 4 weeks.

[0105] Basic nutrient solution: A basic nutrient solution prepared according to the nutrients required for crop growth and suitable for the crop.

[0106] Antifreeze example:

[0107] The antifreeze compositions prepared in Examples 1 to 5 were used to conduct efficacy tests.

[0108] Control group: Crops were treated with an equal amount of water.

[0109] III. Test Equipment

[0110] Illuminated incubator: can precisely control temperature, light intensity and light duration.

[0111] Sprayer: Used to evenly spray antifreeze solution.

[0112] Electronic balance: Used for accurately weighing test materials.

[0113] Vernier calipers: used to measure indicators such as crop leaf thickness.

[0114] Chlorophyll meter: measures the chlorophyll content of leaves.

[0115] Conductivity meter: measures the conductivity of plant tissue extracts to assess the degree of cell membrane damage.

[0116] IV. Test Procedure

[0117] Experimental grouping: Crop seedlings with uniform growth were randomly divided into 6 groups of 10 seedlings each, and were labeled as control group, formulation A group, formulation B group, formulation C group, formulation D group, and formulation E group (corresponding to the control group, the antifreeze compositions of preparation examples 1 to 5, respectively).

[0118] Pretreatment: Place the crop seedlings in a light incubator, set the temperature to 25℃, the light intensity to 2000 Lux, and the light duration to 16 hours / day, and allow them to adapt for 3 days.

[0119] Spraying antifreeze: One day before the low temperature treatment, the crop seedlings of formula A, formula B, formula C, formula D and formula E were sprayed evenly with the corresponding antifreeze solution until the leaf surface was moist but without dripping; the control group was sprayed with an equal amount of water.

[0120] Low temperature treatment: 24 hours after spraying, six groups of crop seedlings were placed in a light incubator set at -10℃ for 12 hours, and then restored to the normal incubation environment of 20℃. The growth status of the crops was observed and recorded.

[0121] V. Indicator Measurement:

[0122] Visual observation: Record changes in the color of crop leaves and whether there are symptoms such as wilting or drying.

[0123] Leaf thickness measurement: Use vernier calipers to measure the thickness of crop leaves. Measure 5 leaves per group and take the average value.

[0124] Chlorophyll content determination: The chlorophyll content of the leaves was measured using a chlorophyll meter. Five leaves were measured for each group, and the average value was taken.

[0125] Electrical conductivity determination: Take 2g of crop leaves, cut them into small pieces, put them into a test tube containing 20mL of distilled water, soak for 2 hours, and then use an electrical conductivity meter to measure the electrical conductivity of the leachate. Each group was measured 3 times, and the average value was taken.

[0126] VI. Experimental Results and Analysis

[0127] 1. Visual observation results:

[0128] The wheat leaves in the control group turned yellow and wilted significantly after low-temperature treatment. Most leaves showed signs of dehydration, indicating significant frost damage, stunted growth, and some wheat died.

[0129] In Formula A, some wheat leaves turned yellow, showed slight wilting, and appeared dehydrated, with the leaves curling slightly.

[0130] In Formula B, the wheat leaves showed yellowing edges and slight wilting. A small number of leaves curled slightly. Dehydration was not obvious, and the leaves enlarged. No wheat died.

[0131] In formulation C, the wheat leaves showed yellowing edges and slight wilting. A small number of leaves exhibited slight curling, but dehydration was not obvious. The leaves were enlarged, similar to those in formulation B.

[0132] The wheat leaves in formula D remained mostly green, with no obvious wilting or drying, no dehydration, and noticeable thickening of the leaves, indicating good wheat development.

[0133] The wheat leaves in formulation E remained mostly green, showing no significant difference from those in formulation D.

[0134] 2. Blade thickness measurement results:

[0135] Group Blade thickness (mm) control group 0.18 Formula A 0.22 Formula B 0.24 Formula C 0.24 Formula D 0.26 Formula E 0.26

[0136] It can be seen that the leaf thickness of crops treated with antifreeze was increased compared to the control group, with the most significant increase observed in formulations D and E. This suggests that formulations D and E may help enhance the crop's frost resistance by increasing leaf thickness, thereby reducing cell damage caused by low temperatures. 3. Chlorophyll content determination results:

[0137] Group Chlorophyll content (mg / g) control group 1.0 Formula A 1.3 Formula B 1.4 Formula C 1.4 Formula D 1.6 Formula E 1.6

[0138] The chlorophyll content of crop leaves treated with antifreeze was higher than that of the control group, indicating that antifreeze can protect the photosynthetic system of crop leaves to a certain extent and reduce the damage of low temperature to chlorophyll. Among them, the chlorophyll content of formulations D and E was the highest, indicating that they had the best protective effect on crop photosynthesis.

[0139] 4. Conductivity measurement results:

[0140] Group Electrical conductivity (μs / cm) control group 200 Formula A 150 Formula B 130 Formula C 130 Formula D 110 Formula E 110

[0141] The conductivity of the control group was significantly higher than that of the other groups, indicating that the cell membranes of the crop leaves in the control group were severely damaged at low temperatures, resulting in a large amount of intracellular substances leaking out. In contrast, the conductivity of the groups using antifreeze was lower, especially the formulations D and E, indicating that formulations D and E can better protect the integrity of crop cell membranes and reduce cell damage.

[0142] VII. Conclusion

[0143] Based on the above experimental results, under the conditions of this experiment, crop antifreeze formulations D and E showed the best frost protection effect on crops. They effectively reduced leaf damage at low temperatures, maintained normal leaf physiological functions, and improved the crop's frost resistance. Formulations B and C also had some frost protection effect, but were slightly less effective than formulations D and E. In actual agricultural production, appropriate crop antifreeze formulations can be selected based on the crop type and local climate conditions, referring to the results of this experiment, to mitigate the damage of low temperatures to crops and improve crop yield and quality.

[0144] How to use

[0145] Application Timing: For plants grown outdoors, the optimal application time is 7 to 10 days before the first cold snap of the year in the local area. At this time, the plants have not yet been severely stressed by low temperatures and can fully absorb the active ingredients in the antifreeze, activating their own cold-resistance mechanisms. For plants grown in greenhouses, antifreeze can be applied when the temperature inside the greenhouse remains below 10°C for 3 consecutive days, building a cold-resistance barrier for the plants in advance. For perennial plants such as trees, application 2 to 3 weeks before leaf fall in autumn can help the plants store enough cold-resistance substances to successfully survive the long winter; for annual plants such as vegetables, application should be done in the middle and later stages of growth, before the expected arrival of cold weather.

[0146] Dilution Ratio: The dilution ratio of the antifreeze needs to be adjusted flexibly according to different types of plants and environmental conditions. Generally, this antifreeze composition should be diluted 300 to 500 times before use. For plant varieties with weak cold resistance, such as some tropical flowers, a 300-fold dilution can be used to ensure sufficient concentration of active ingredients to enhance their cold resistance; for plants with relatively strong cold resistance, such as some northern deciduous trees, a dilution of up to 500 times can be used. In extreme low-temperature environments, such as when the temperature may drop below -10℃, the dilution ratio can be appropriately reduced to 250 times to enhance the protective effect; while in relatively mild low-temperature environments, such as when the expected minimum temperature is around 0℃, the dilution ratio can be increased to 550 times.

[0147] Application methods: Primarily foliar spraying and root drenching. For foliar spraying, use a spraying device with good atomization, such as a backpack sprayer or electric sprayer, to ensure that the diluted antifreeze evenly covers both sides of the plant leaves. Leaves are important organs for gas exchange and photosynthesis in plants; even application allows the active ingredients to quickly enter the plant through the leaf stomata. For tall trees, high-pressure spraying equipment can be used to ensure that the agent reaches all parts of the plant. For root drenching, slowly pour the diluted antifreeze around the plant's root system, ensuring that the agent penetrates the main areas where the roots are distributed. Roots are the key site for water and nutrient absorption in plants, efficiently absorbing the active ingredients in the antifreeze and transporting them throughout the plant via transpiration. For potted plants, the diluted solution can be directly poured into the pot until a small amount of liquid flows out from the bottom, ensuring that the roots are fully in contact with the agent.

[0148] Example 2: Citrus Antifreeze Test

[0149] Experimental materials: Citrus trees with similar growth conditions and the same age were selected and planted in orchards with the same soil, light and irrigation conditions.

[0150] Experimental Methods: Citrus plants were randomly divided into two groups of 40 plants each. The control group received traditional mulching with dry straw for cold protection without the antifreeze composition of this invention. Ten days before the onset of winter cold, the experimental group received the antifreeze composition prepared in Example 5 of this invention, diluted 300 times, for foliar spraying and trunk application, repeated every 7 days for a total of 3 times. During the experiment, both groups maintained consistent daily management practices, including fertilization and pest and disease control.

[0151] Experimental Results: After experiencing a cold wave, the leaves of the control group citrus plants suffered extensive frost damage, with a frost damage rate reaching 40%, and some branches were also damaged, affecting flowering and fruiting the following year. In contrast, the frost damage rate of the leaves in the experimental group citrus plants was only 10%, and the branches and trunks were largely unaffected by frost. Physiological indicators of the two groups of citrus plants were tested, and the chlorophyll content, soluble sugar content, and antioxidant enzyme activity in the leaves of the experimental group were significantly higher than those in the control group. This indicates that the photosynthetic capacity and stress resistance of the experimental group plants were effectively improved. The antifreeze composition of this invention can significantly enhance the frost resistance of citrus plants and reduce the damage caused by low-temperature freezing.

[0152] Example 3 of efficacy: Frost resistance test of flowers

[0153] Experimental materials: Healthy tulip plants were selected and planted in a greenhouse, where temperature, humidity and light conditions were kept constant.

[0154] Experimental method: Different concentrations of antifreeze were prepared in Example 5, forming treatment groups and control groups (sprayed with water). For example, the antifreeze was diluted to 200 times, 400 times, 500 times, 800 times, and 1000 times, with 20 flower plants used in each treatment group.

[0155] Plant treatment: Transplant the selected tulip plants into flowerpots of the same size and cultivate them under normal conditions (suitable temperature, light, water, etc.) for one week to allow them to adapt to the new environment.

[0156] Antifreeze application: 3-5 days before the onset of low temperatures, spray the tulip plants in each treatment group with the appropriate concentration of antifreeze, ensuring the leaf surface is evenly moistened but not dripping wet. The control group was sprayed with an equal amount of water. Spraying should be carried out on a sunny morning between 9 and 11 am.

[0157] Low-temperature treatment: After spraying with antifreeze, all tulip plants were transferred to an artificial climate chamber or other temperature-controlled environment to simulate a low-temperature environment. The low-temperature treatment was set at -5℃ for 24 hours. During the low-temperature treatment, the ambient temperature was monitored in real time using a thermometer and recorded.

[0158] Recovery Cultivation: After the low-temperature treatment, the flower plants are moved back to a normal environment for recovery cultivation, maintaining suitable temperature, light, and water conditions. Observe the recovery of the flower plants.

[0159] Observation indicators

[0160] Severity of frost damage: On the 1st, 3rd, and 7th day after the end of the low-temperature treatment, observe the frost damage symptoms of the flower plants and classify them according to the following standards:

[0161] Level 0: No signs of frost damage, and the plant is growing normally.

[0162] Grade 1: Leaves are slightly curled, and a few leaves show slight yellowing at the edges.

[0163] Level 2: The leaves are noticeably curled, and some leaves have large areas of yellowing and withering, but the stems have not been damaged by frost.

[0164] Level 3: Most leaves turn yellow and fall off, and the stems show slight frost damage symptoms (such as discoloration and softening).

[0165] Level 4: Plant dead.

[0166] Calculate the frost damage index for each treatment group: Frost damage index = Σ(Number of plants damaged at each level × Representative value at each level) / (Total number of plants surveyed × Representative value at the highest level) × 100%.

[0167] Experimental Results: Data Recording of Frost Damage Injuries to Flowers in Different Treatment Groups

[0168]

[0169] The frost damage index shows that the frost damage index of tulip plants decreased significantly after the use of antifreeze. However, the decrease was not significant when the frost damage index was 200-500 times diluted. Considering the cost of the pesticide, it is recommended to use a dosage of 500-1000 times diluted pesticide in production.

[0170] After 24 hours of low-temperature treatment, the tulips in the control group showed obvious frost damage, with petals discoloring and wilting, and significantly reduced flower opening, severely impairing their ornamental value. In contrast, the tulips in the experimental group maintained a relatively normal open state, with vibrant petals and less frost damage. The frost damage index decreased by 50%. Observation of the cell structure of the five groups of plants revealed that the cell membranes of the experimental group were more intact, and the organelle structures within the cells were clearly defined, while the cell membranes of the control group cells were ruptured, and organelles were severely damaged. This fully demonstrates that the antifreeze composition of this invention can effectively protect the cell structure of plants under low-temperature conditions, improve the frost resistance of flowers, and maintain their ornamental quality.

[0171] The beneficial effects of this invention are:

[0172] (1) Creatively, polyvinyl alcohol and alginic acid are polymerized through an initiator to form a protective film-forming agent for use as a plant antifreeze agent. This protects plants from the erosion of low temperatures and does not affect the photosynthesis of plants. The materials used are easily degradable, environmentally friendly and safe, and leave no residue.

[0173] (2) Potassium lactate and potassium phosphite are creatively used as plant antifreeze agents, which can kill bacteria and fungi, promote crop maturation, increase cellulose and lignin content, and supplement potassium.

[0174] (3) Glutamic acid betaine is creatively used as a plant antifreeze agent. Glutamic acid betaine is a natural organic acid commonly found in many crops. It can provide plants with stress resistance, making them more adaptable to environmental changes. In the event of disasters such as drought, frost damage, or pests and diseases, it can make crops more adaptable to environmental changes, thereby reducing their environmental burden. At the same time, in this invention, it can also be used as an emulsifier in the process to ensure product stability.

[0175] Significantly Enhances Plant Freeze Resistance: Through scientifically designed components and precise manufacturing processes, the antifreeze composition of this invention can enhance the freeze resistance of plants on multiple levels. Tests on various plants show that after using the antifreeze composition of this invention, the degree of freeze damage to plants in low-temperature environments is significantly reduced, with an average increase in freeze resistance of 40%-60%, effectively ensuring the normal growth and development of plants under low-temperature stress.

[0176] High safety: The antifreeze composition of this invention is derived from natural plant extracts and nutrients and compounds that are harmless to the human body and the environment. It does not contain any harmful chemicals, has no risk of pesticide residues, and has no negative impact on the soil environment, water environment, or the quality and safety of agricultural products. It meets the development requirements of green agriculture and ecological environmental protection.

[0177] Low cost: The raw materials for preparing the antifreeze composition of this invention are widely available and relatively inexpensive. The preparation process is simple and easy to operate, and does not require complex and expensive equipment and high-end technology, which effectively reduces production costs and is conducive to large-scale promotion and application in agricultural production, making it acceptable to the majority of growers.

[0178] Wide Applicability: Extensive field trials and practical application verification have shown that the antifreeze composition of this invention is suitable for a wide variety of plants, including various crops, fruit trees, flowers, and landscaping plants. Whether in the frigid northern regions or the southern areas prone to low-temperature freezing damage, and whether the plants are grown outdoors or in greenhouses, it achieves excellent frost protection, demonstrating high versatility and application value.

Claims

1. A plant-based antifreeze composition, characterized in that, Include Film-forming agent 1-5% Film-forming initiator 0.3–1.5% Phosphorus and potassium fertilizer 5-15% Antifreeze 1-5% Water balance The film-forming agent is polyvinyl alcohol and sodium alginate; the film-forming initiator is at least one of potassium persulfate, azobisisobutyronitrile, and cumene hydrogen peroxide; the phosphorus and potassium fertilizer is at least one of potassium phosphite and potassium dihydrogen phosphate, with a content of [missing information]; the antifreeze is at least one of ethylene glycol, α-propylene glycol, and glycerol.

2. The plant-based antifreeze composition according to claim 1, characterized in that... It further contains biostimulants, among which Film-forming agent 1-5% Film-forming initiator 0.3–1.5% Phosphorus and potassium fertilizer 5-15% Antifreeze 1-5% Biostimulants 4-18% Water balance The biostimulant is composed of mineral-derived potassium humate, fish protein, chitosan (a chitin derivative), and amino acids, with the following contents: 1-10% mineral-derived potassium humate, 1-3% fish protein, 1-2% chitosan (a chitin derivative), and 1-3% amino acids. Specifically, the amino acids are two or more of valine, polyglutamic acid, tryptophan, and serine.

3. The plant antifreeze composition according to claim 1 further contains a bio-fungicide, wherein... Film-forming agent 1-5% Film-forming initiator 0.3–1.5% Phosphorus and potassium fertilizer 5-15% Antifreeze 1-5% Biological fungicide 1-5% Water balance The biocidal agent is lactic acid and its salt, preferably potassium lactate.

4. The plant antifreeze composition according to claim 1, further comprising a plant growth regulator, wherein: Film-forming agent 1-5% Film-forming initiator 0.3–1.5% Phosphorus and potassium fertilizer 5-15% Antifreeze 1-5% Plant growth regulators 1–2.01% Water balance The plant growth regulators are 14-hydroxybrassinolide and tetramethylglutaric acid; their contents are 0.0075-0.01% for 14-hydroxybrassinolide and 1-2% for tetramethylglutaric acid.

5. The plant-based antifreeze composition according to claim 1, further comprising a biosurfactant, wherein... Film-forming agent 1-5% Film-forming initiator 0.3–1.5% Phosphorus and potassium fertilizer 5-15% Antifreeze 1-5% Biosurfactants 1-8% Water balance The biosurfactant is glutamate betaine.

6. The plant-based antifreeze composition according to claims 1-5, wherein it contains, Film-forming agent 1-5% Film-forming initiator 0.3–1.5% Phosphorus and potassium fertilizer 5-15% Antifreeze 1-5% Biostimulants 4-18% Biological fungicide 1-5% Plant growth regulators 1–2.01% Biosurfactants 1-8% Water balance in, The film-forming agent is polyvinyl alcohol-alginic acid / sodium, with a content of 1-5%; the film-forming agent is polymerized by at least one of the film-forming initiators potassium persulfate, azobisisobutyronitrile, and cumene hydrogen peroxide; the phosphorus and potassium fertilizer is at least one of potassium phosphite and potassium dihydrogen phosphate; the antifreeze is at least one of ethylene glycol, α-propylene glycol, and glycerol; the biostimulant is composed of mineral-derived potassium humate, fish protein, and chitosan, a chitin derivative, with contents of: 1-10% mineral-derived potassium humate, 1-3% fish protein, and 1-3% chitin, respectively. The biostimulant includes 1-2% chitosan derivatives; the biostimulant also includes amino acids, specifically two or more combinations of valine, polyglutamic acid, tryptophan, and serine, with a total content of 1-3%; the biofungicide is lactic acid and its salt, preferably potassium lactate; the plant growth regulator is 14-hydroxybrassinolide and tetramethylglutaric acid, with contents of 0.0075-0.01% for 14-hydroxybrassinolide and 1-2.01% for tetramethylglutaric acid; and the biosurfactant is glutamic acid betaine.

7. A method for preparing the plant-based antifreeze composition according to any one of claims 1 to 6, characterized in that, S1: First, polyvinyl alcohol is mixed with alginate / sodium to prepare a biofilm-forming agent in the presence of a film-forming initiator; S2: Dissolve the polar components in water to prepare an aqueous solution. The polar components are: phosphorus and potassium fertilizer, biostimulant and bio-fungicide. S3: Mix the antifreeze or antifreeze containing plant growth regulators with the aqueous solution of S2 above to form a solution; for the above mixed solution, if necessary, add a biosurfactant to emulsify the solution; S4: Add the biofilm-forming agent prepared in step S1 to the mixed solution obtained in S3 to prepare the antifreeze composition.

8. The use of the plant antifreeze composition according to any one of claims 1 to 6, or the use of the composition obtained by the preparation method according to claim 7, is the application of the above composition in plant antifreeze and frost protection, wherein the plants include field crops, fruit trees, vegetables and garden plants that require frost protection.

9. The use according to claim 8, characterized in that, The composition is applied by spraying the composition solution.

10. The method according to claim 9, characterized in that, When using the spray, apply at -10℃ to 5℃, once every 7 to 15 days, for 1 to 3 consecutive applications; the spray should be a 100 to 4000 times, preferably 500 to 1000 times, dilution of the composition.

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