CN116640289A - Polyurethane material for controlled release fertilizer coating and preparation method and application thereof - Google Patents

Polyurethane material for controlled release fertilizer coating and preparation method and application thereof Download PDF

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Publication number
CN116640289A
CN116640289A CN202310002816.7A CN202310002816A CN116640289A CN 116640289 A CN116640289 A CN 116640289A CN 202310002816 A CN202310002816 A CN 202310002816A CN 116640289 A CN116640289 A CN 116640289A
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parts
controlled release
release fertilizer
polyurethane material
fertilizer coating
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CN116640289B (en
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龚岳
朱鑫玉
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Anhui Zhuoli Agricultural Technology Co ltd
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Anhui Zhuoli Agricultural Technology Co ltd
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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
    • C05G5/37—Layered or coated, e.g. dust-preventing coatings layered or coated with a polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/6705—Unsaturated polymers not provided for in the groups C08G18/671, C08G18/6795, C08G18/68 or C08G18/69
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
    • Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures

Abstract

The invention provides a polyurethane material for a controlled release fertilizer coating, and a preparation method and application thereof, wherein the polyurethane material for the controlled release fertilizer coating comprises the following raw materials in parts by weight: 40-50 parts of modified castor oil-based polyol, 40-50 parts of isocyanate, 15-20 parts of straw slag powder liquefier, 5-10 parts of flame retardant, 5-10 parts of antistatic agent and 5-10 parts of emulsifier. The preparation method comprises the following steps: 1) Adding the modified castor oil-based polyol and isocyanate into a container, and stirring and mixing uniformly at constant temperature; 2) And (2) adding the straw slag powder liquefact, the flame retardant, the antistatic agent and the emulsifier into the solution obtained in the step (1), continuously stirring, and vacuum defoaming after uniformly mixing to obtain the product, namely the polyurethane material for the controlled release fertilizer coating. The polyurethane material for the controlled release fertilizer coating has good hydrophobicity and mechanical property, good weather resistance at high temperature, low raw material cost and degradability, has good slow release property when used for the controlled release fertilizer, and has good application prospect in the technical field of the controlled release fertilizer coating.

Description

Polyurethane material for controlled release fertilizer coating and preparation method and application thereof
Technical Field
The invention relates to the technical field of controlled release fertilizer coating, in particular to a polyurethane material for fertilizer coating and a preparation method and application thereof.
Background
With the continuous development of human society, the world population is rapidly increased, the grain demand is greatly increased, and the improvement of crop yield and the guarantee of grain safety become important points of agricultural development. The fertilizer is the basis of agriculture, and the use of the fertilizer has become one of important measures for promoting the yield increase of agriculture. The traditional fertilizer has low utilization rate, and excessive use not only can cause economic loss, but also can bring negative influence to the environment. The slow-release fertilizer is a novel fertilizer capable of meeting the requirements of crops, and refers to a fertilizer which meets the national regulation standard in a broad sense and greatly prolongs the nutrient release period, and refers to a fertilizer with the nutrient release rate meeting the growth rule of crops in a narrow sense, namely, being basically consistent with the nutrient rate required or absorbed by the growth period of crops. According to different production processes, a plurality of different types of products are appeared on the market, mainly including coated type, synthetic type, chemical inhibition type, matrix composite type, adhesive type and the like, wherein the nutrient release rate of the coated fertilizer is more consistent with the nutrient requirements of crops, and the sustained and controlled release effect is optimal. The coating materials of the coated fertilizer mainly comprise three types: the organic polymer coating material is widely accepted by researchers at present and can realize the synchronization of nutrient release and crop demands to the greatest extent. Coating materials are generally classified into natural polymers, synthetic polymers and semisynthetic polymer coating materials. The natural polymer coating material mainly comprises starch, humic acid, chitosan, sodium alginate, cellulose, lignin and the like, has the characteristics of wide sources, no toxicity, low cost, easy acquisition, environmental friendliness and the like, but has the defects that the material is easy to degrade by microorganisms due to the self property, and has poor slow release performance. The semi-synthetic polymer coating material is mainly obtained by modifying natural polymer materials, and the coating material mainly comprises crosslinked starch, ethyl cellulose, cellulose derivatives and the like, while the synthetic polymer coating material mainly comprises resins and olefins, such as thermoplastic resins like polyethylene, polypropylene, polyvinyl alcohol, polyurethane, alkyd resin and thermosetting resins like urea-formaldehyde resin.
Polyurethane was first invented by the german chemist Bayer in the 30 th century and rapidly entered the market in the 40 th year with both types of products, elastomers and foams, soon taking up a non-trivial place in the market. Today, the product types of polyurethane materials mainly include elastomers, foams, adhesives/sealants, coatings, leather slurries, spandex, and the like. Because the raw materials of the traditional polyurethane are non-renewable petroleum resources, the environment is greatly damaged, and the petroleum resources are increasingly deficient along with continuous exploitation of human beings, the polyurethane has the new direction of development of renewable, environment-friendly and healthy bio-based polyurethane as polyurethane materials. Because vegetable oil acquisition channels are various, the processing technology is simple and the price is low, and vegetable-based polyurethane becomes one of the focus of great researchers.
Chinese patent CN113999361A discloses a plant-based polyurethane material and a preparation method thereof, wherein Chinese herbal medicine straws with functions of tranquillizing, health care and the like, such as crop straws of shizandra berry, industrial hemp, roman chamomile, purple perilla and the like, are used as raw materials, chinese herbal medicine straw-based plant polyol is prepared through a green chemical process, and the ecological polyurethane material is obtained based on the Chinese herbal medicine straw-based plant polyol, but the mechanical strength and weather resistance of the prepared ecological polyurethane material are required to be further improved. Chinese patent CN111471173A discloses a method for preparing polyether polyol by straw catalytic solvothermal liquefaction, which takes straw powder as a raw material, starch-based polyether polyol as a liquefying agent, micromolecular sulfoacid as a catalyst and sodium polyaspartate as a dispersing agent, and the reaction is carried out for 3-9 hours at 120-180 ℃ to prepare polyether polyol, so that the reaction time for preparing polyol by straw is longer, the liquefying rate of the method is low and is not more than 70%, and the waste of energy and raw materials is larger.
Therefore, in order to better meet the actual needs, it is necessary to provide an environment-friendly and economical polyurethane material for the controlled release fertilizer coating, which has good mechanical strength and weather resistance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an environment-friendly and economic polyurethane material for the controlled release fertilizer coating, which has good mechanical strength and weather resistance at the same time, so as to meet the requirements of practical application.
To achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a polyurethane material for a controlled release fertilizer coating, which comprises the following raw materials in parts by weight: 40-50 parts of modified castor oil-based polyol, 40-50 parts of isocyanate, 15-20 parts of straw slag powder liquefier, 5-10 parts of flame retardant, 5-10 parts of antistatic agent and 5-10 parts of emulsifier.
In some embodiments of the invention, the modified castor oil-based polyol comprises the following raw materials in parts by weight: 10-20 parts of regenerated microcrystal, 20-30 parts of castor oil, 20-30 parts of diethanolamine, 5-10 parts of antioxidant and 1-5 parts of catalyst.
In some embodiments of the invention, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1035, antioxidant 1076, triphenyl phosphite, and trisnonylphenyl phosphite.
In some embodiments of the invention, the catalyst is selected from one or more of tetrabutyl titanate, tetraisopropyl titanate, organotin, and organobismuth.
In some embodiments of the invention, the regenerated microcrystal particle size is 20-40 μm (e.g., may be 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm, 31 μm, 32 μm, 33 μm, 34 μm, 35 μm, 36 μm, 37 μm, 38 μm, 39 μm, 40 μm, or any value therein), and the degree of polymerization is 60-80 (e.g., may be 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, or any value thereof), and the method of making the same comprises the steps of:
(1) Pulverizing herba Salsolae Collinae leaves, decocting in boiling water for 5-10min, filtering to obtain residue, adding 3-5% potassium hydroxide solution to adjust pH to 10-12, filtering, washing the residue to neutrality, adding distilled water to adjust pH to 1-2 with 5-10% hydrochloric acid, heating to 50-70deg.C in water bath, adding absolute ethanol, dehydrating, and leaching at room temperature for 4-5 hr;
(2) Drying the filter residue obtained in the step (1) at 45-55 ℃, crushing, sieving with a 70-80 mesh sieve, adding into sulfuric acid with the concentration of 40-60%, treating in a shaking table at 45-55 ℃ for 2-3 hours, centrifuging, washing to neutrality, drying the obtained suspension to constant weight at 40-50 ℃, and crushing into powder;
(3) Preparing NaOH/urea mixed aqueous solution (wherein the mass fraction of NaOH is 3-5% and the mass fraction of urea is 5-10%), pre-cooling to-10 to-5 ℃, adding the powder obtained in the step (2), continuously stirring, adding absolute ethyl alcohol, stirring for 1-2h, and centrifugally separating to obtain the product which is the regenerated microcrystal.
In some embodiments of the invention, the mass of the absolute ethanol in step (1) is 2-3 times that of the residue; the quality of the sulfuric acid in the step (2) is 2-3 times of that of the filter residue; the mass of the NaOH/urea mixed aqueous solution in the step (3) is 10-15 times of that of the powder obtained in the step (2), and the mass of the absolute ethyl alcohol is 2-3 times of that of the powder obtained in the step (2).
In some embodiments of the invention, the modified castor oil-based polyol preparation method comprises the steps of:
(1) Heating and steaming castor oil raw materials, stirring to reduce the temperature, and adding diethanolamine and a catalyst for reaction;
(2) Adding regenerated microcrystal and antioxidant into the solution obtained in the step (1), and continuously stirring for 1-2h to obtain a product, namely the modified castor oil-based polyol.
In the method for producing a modified castor oil-based polyol of the present invention, the spin-steaming temperature in the step (1) is 100 to 120 ℃ (for example, may be 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, 110 ℃, 111 ℃, 112 ℃, 113 ℃, 114 ℃, 115 ℃, 116 ℃, 117 ℃, 118 ℃, 119 ℃, 120 ℃ or any value thereof); the steaming time is 10-12h (for example, 10h, 10.5h, 11h, 11.5h, 12h or any value thereof).
In the method for producing a modified castor oil-based polyol of the present invention, the reaction temperature in the step (1) may be 60 to 80 ℃ (for example, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃ or any value thereof).
In some embodiments of the invention, the straw slag powder liquefier is formed by mixing straw powder liquid and propanol acid, wherein the straw powder liquid accounts for 50-70% and the propanol acid accounts for 30-50%.
In some embodiments of the present invention, the method for preparing the straw powder liquid comprises the following steps:
(1) PEG600, concentrated sulfuric acid and glycerin are added into a container, and stirred and mixed uniformly;
(2) Adding corn stalk powder into the solution obtained in the step (1), heating to react, and adding alkali to adjust the pH value to be neutral after the reaction is finished, wherein the obtained product is stalk powder liquid.
In the preparation method of the straw powder liquid, the mass ratio of the corn straw powder to the PEG600 to the glycerol is 1:2-3:3-5 (e.g., may be 1:2:3, 1:2:4, 1:2:5, 1:3:3, 1:3:4, 1:3:5, or any value therein).
In the preparation method of the straw powder liquid, the mass of the concentrated sulfuric acid is 1-2% of the total mass of the corn straw powder, the PEG600 and the glycerol.
In the method for producing a straw powder liquid according to the present invention, the reaction temperature in the step (2) is 140 to 160 ℃ (for example, 140 ℃, 141 ℃, 142 ℃, 143 ℃, 144 ℃, 145 ℃, 146 ℃, 147 ℃, 148 ℃, 149 ℃, 150 ℃, 151 ℃, 152 ℃, 153 ℃, 154 ℃, 155 ℃, 156 ℃, 157 ℃, 158 ℃, 159 ℃, 160 ℃ or any temperature value thereof); the reaction time is 1-2h (e.g., 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2h, or any temperature value therein).
In some embodiments of the invention, the isocyanate is selected from one or more combinations of 4-toluene diisocyanate, 2, 6-toluene diisocyanate, isophorone diisocyanate, and terephthal-diisocyanate;
in some embodiments of the invention, the flame retardant is selected from one or more of magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, melamine cyanurate.
In some embodiments of the invention, the antistatic agent is selected from the group consisting of a Hirsch XQL-K antistatic agent or a Jining North Jia LS antistatic agent.
In some embodiments of the invention, the emulsifier is selected from one or more of sodium stearate, sodium lauryl sulfate, sorbitan monooleate, polysorbate methylcellulose and sodium carboxymethylcellulose.
The preparation method of the polyurethane material for the controlled release fertilizer coating comprises the following steps:
(1) Adding the modified castor oil-based polyol and isocyanate into a container, maintaining the temperature at 75-85 ℃, stirring and mixing uniformly, and reacting;
(2) And (3) adding the straw slag powder liquefact, the flame retardant, the antistatic agent and the emulsifier into the solution obtained in the step (1), continuously stirring, and carrying out vacuum defoaming after uniformly mixing to obtain the product, namely the polyurethane material for the controlled release fertilizer coating.
The application method of the polyurethane material for the controlled release fertilizer coating in the technical field of the controlled release fertilizer coating comprises the following steps:
(1) Adding fertilizer into a coating pot, heating to 65-70 ℃, and keeping the rotating speed of the coating pot at 30-35r/min;
(2) Spraying a polyurethane material coating material for coating the controlled release fertilizer on the surface of the fertilizer in proportion, and adding talcum powder after coating is finished, wherein the obtained product is the controlled release fertilizer;
in some embodiments of the invention, the fertilizer in step (1) has a particle size of 2-4.75mm (e.g., may be 2mm, 2.2mm, 2.4mm, 2.6mm, 2.8mm, 3mm, 3.2mm, 3.4mm, 3.6mm, 3.8mm, 4mm, 4.2mm, 4.4mm, 4.6mm, 4.75mm, or any value therein), the spraying process in step (2) is performed 3-4 times at 3-5min intervals (e.g., may be 3min, 3.5min, 4min, 4.5min, 5min, or any value therein), and the polyurethane material for controlled release fertilizer coating has a coating material mass of 2.1-3% (e.g., may be 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3% or any value therein) of the fertilizer mass.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the polyurethane material for the controlled release fertilizer coating, the regenerated microcrystal is combined with the castor oil-based polyol to carry out grafting modification, so that the obtained modified castor oil-based polyol can form a strong hydrogen bond network in the preparation process of polyurethane, the hydrophobicity of the polyurethane material is effectively improved, and meanwhile, the regenerated microcrystal has good compatibility, so that the prepared polyurethane material has the advantages of improved tensile strength, good toughness and good mechanical property.
(2) According to the polyurethane material for the controlled-release fertilizer coating, the straw slag powder liquefier is added in the preparation process, the molecule of the polyurethane material contains more phenolic hydroxyl groups, the reactivity is high, and the polyurethane material can be combined with isocyanate in a reaction way, so that the sensitivity of the polyurethane material to temperature is reduced, and the prepared polyurethane material for the controlled-release fertilizer coating has good weather resistance at high temperature.
(3) The polyurethane material for the controlled-release fertilizer coating provided by the invention has the advantages that the raw materials used in the preparation process are renewable, low in cost and degradable, the technical scheme of resource conservation and environmental friendliness is realized, the raw material requirement of the controlled-release fertilizer on the polyurethane material can be met, the controlled-release fertilizer prepared by using the polyurethane material for the controlled-release fertilizer coating has good slow release property, the release speed of the fertilizer is more gentle and uniform, the release period can be effectively prolonged, the nutrient requirement of crops with longer growing season in the whole growing season can be met, and the defects in the application of the prior art can be well solved by replacing polyurethane prepared by the traditional petroleum-based polyester polyol.
Detailed Description
The invention will be described below in connection with specific embodiments. The following examples are illustrative of the present invention and are not intended to limit the present invention. Other combinations and various modifications within the spirit of the invention may be made without departing from the spirit or scope of the invention. In the examples below, the compounds used and the related reagents are all commercially available, with the polyester polyol Dynacoll7110 being purchased from the International trade company of Xianshihui, guangzhou.
Preparation of regenerated microcrystals
(1) Pulverizing 100g of herba Salsolae Collinae leaves, adding into boiling water, decocting for 8min, filtering to obtain residue, regulating pH to 11 with 3% potassium hydroxide solution, filtering, washing the obtained residue to neutrality, adding into 200g of distilled water, regulating pH to 2 with 10% hydrochloric acid, heating to 50deg.C, adding 200g of absolute ethanol, dehydrating, and leaching at room temperature for 4 hr;
(2) Drying the filter residue obtained in the step (1) at 55 ℃, crushing, sieving with a 70-mesh sieve, adding into 200g of sulfuric acid with the concentration of 60%, treating for 2 hours in a shaking table at 55 ℃, centrifuging, washing to neutrality, drying the obtained suspension to constant weight at 40 ℃, and crushing into powder;
(3) Preparing 1000g of NaOH/urea mixed aqueous solution (wherein the mass fraction of NaOH is 5% and the mass fraction of urea is 10%), pre-cooling to-10 ℃, adding the powder obtained in the step (2), continuously stirring, adding 200g of absolute ethyl alcohol, stirring for 2h, and centrifugally separating to obtain a product which is the regenerated microcrystal.
Preparation of modified castor oil based polyol I
The modified castor oil-based polyol comprises the following raw materials in parts by weight: 20 parts of regenerated microcrystal, 30 parts of castor oil, 30 parts of diethanolamine, 1010 10 parts of antioxidant and 5 parts of tetrabutyl titanate.
The preparation method comprises the following steps:
(1) Heating and steaming castor oil raw material at 120 ℃ for 10 hours, stirring and reducing the temperature to 80 ℃, and adding diethanolamine and tetrabutyl titanate for reaction;
(2) Adding regenerated microcrystal and antioxidant 1010 into the solution obtained in the step (1), and continuously stirring for 2 hours to obtain a product, namely the modified castor oil-based polyol I.
Preparation of modified castor oil-based polyol II
The modified castor oil-based polyol comprises the following raw materials in parts by weight: 10 parts of regenerated microcrystal, 20 parts of castor oil, 20 parts of diethanolamine, 5 parts of antioxidant 1010 and 1 part of tetrabutyl titanate.
The preparation method comprises the following steps:
(1) Heating and steaming castor oil raw material at 120 ℃ for 10 hours, stirring and reducing the temperature to 80 ℃, and adding diethanolamine and tetrabutyl titanate for reaction;
(2) And (3) adding regenerated microcrystal and antioxidant 1010 into the solution obtained in the step (1), and continuously stirring for 2 hours to obtain a product, namely the modified castor oil-based polyol II.
Preparation of straw powder liquid I
The preparation method comprises the following steps:
(1) 150g PEG600, 5g concentrated sulfuric acid and 250g glycerin are added into a container, and stirred and mixed uniformly;
(2) Adding 50g of corn straw powder into the solution obtained in the step (1), heating to 150 ℃ for reaction for 2 hours, and adding sodium hydroxide to adjust the pH value to be neutral after the reaction is finished, wherein the obtained product is straw powder liquid I.
Preparation of straw powder II
The preparation method comprises the following steps:
(1) 100g PEG600, 3g concentrated sulfuric acid and 150g glycerin are added into a container, and stirred and mixed uniformly;
(2) Adding 50g of corn straw powder into the solution obtained in the step (1), heating to 150 ℃ for reaction for 2 hours, and adding sodium hydroxide to adjust the pH value to be neutral after the reaction is finished, wherein the obtained product is straw powder liquid II.
Example 1
The polyurethane material for the controlled release fertilizer coating comprises the following raw materials in parts by weight: 50 parts of modified castor oil-based polyol I, 50 parts of 4-toluene diisocyanate, 20 parts of straw slag powder liquefier (formed by mixing 70% of straw powder I and 30% of propanol acid), 10 parts of magnesium hydroxide, 10 parts of Hirschiro (Shanghai) XQL-K antistatic agent and 10 parts of sodium stearate.
The preparation method comprises the following steps:
(1) Adding the modified castor oil-based polyol and the 4-toluene diisocyanate into a container, mixing, keeping the temperature at 75 ℃, and continuously stirring to react;
(2) And (3) adding the straw slag powder liquefier, magnesium hydroxide, the XQL-K antistatic agent and sodium stearate into the solution obtained in the step (1), continuously stirring, and carrying out vacuum defoamation after uniformly mixing, thus obtaining the product, namely the polyurethane material for the controlled release fertilizer coating.
Example 2
The polyurethane material for the controlled release fertilizer coating comprises the following raw materials in parts by weight: 50 parts of modified castor oil-based polyol II, 50 parts of 4-toluene diisocyanate, 20 parts of straw slag powder liquefier (formed by mixing 70% of straw powder liquid I and 30% of propanol acid), 10 parts of magnesium hydroxide, 10 parts of Hirschiro (Shanghai) XQL-K antistatic agent and 10 parts of sodium stearate.
The preparation method is the same as in example 1.
Example 3
The polyurethane material for the controlled release fertilizer coating comprises the following raw materials in parts by weight: 40 parts of modified castor oil-based polyol II, 50 parts of 4-toluene diisocyanate, 20 parts of straw slag powder liquefier (formed by mixing 70% of straw powder liquid I and 30% of propanol acid), 10 parts of magnesium hydroxide, 10 parts of Hirschiro (Shanghai) XQL-K antistatic agent and 10 parts of sodium stearate.
The preparation method is the same as in example 1.
Example 4
The polyurethane material for the controlled release fertilizer coating comprises the following raw materials in parts by weight: 40 parts of modified castor oil-based polyol II, 40 parts of 4-toluene diisocyanate, 20 parts of straw slag powder liquefier (formed by mixing 70% of straw powder liquid I and 30% of propanol acid), 10 parts of magnesium hydroxide, 10 parts of Hirschiro (Shanghai) XQL-K antistatic agent and 10 parts of sodium stearate.
The preparation method is the same as in example 1.
Example 5
The polyurethane material for the controlled release fertilizer coating comprises the following raw materials in parts by weight: 40 parts of modified castor oil-based polyol II, 40 parts of 4-toluene diisocyanate, 20 parts of straw slag powder liquefier (formed by mixing 70% of straw powder II and 30% of propanol acid), 10 parts of magnesium hydroxide, 10 parts of Hirschiro (Shanghai) XQL-K antistatic agent and 10 parts of sodium stearate.
The preparation method is the same as in example 1.
Example 6
The polyurethane material for the controlled release fertilizer coating comprises the following raw materials in parts by weight: 40 parts of modified castor oil-based polyol II, 40 parts of 4-toluene diisocyanate, 20 parts of straw slag powder liquefier (formed by mixing 50% of straw powder II and 50% of propanol acid), 10 parts of magnesium hydroxide, 10 parts of Hirschiro (Shanghai) XQL-K antistatic agent and 10 parts of sodium stearate.
The preparation method is the same as in example 1.
Example 7
The polyurethane material for the controlled release fertilizer coating comprises the following raw materials in parts by weight: 40 parts of modified castor oil-based polyol II, 40 parts of 4-toluene diisocyanate, 15 parts of straw slag powder liquefier (formed by mixing 50% of straw powder II and 50% of propanol acid), 10 parts of magnesium hydroxide, 10 parts of Hirschiro (Shanghai) XQL-K antistatic agent and 10 parts of sodium stearate.
The preparation method is the same as in example 1.
Example 8
The polyurethane material for the controlled release fertilizer coating comprises the following raw materials in parts by weight: 40 parts of modified castor oil-based polyol II, 40 parts of 4-toluene diisocyanate, 15 parts of straw slag powder liquefier (formed by mixing 50% of straw powder II and 50% of propanol acid), 5 parts of magnesium hydroxide, 20 parts of Hirschiro (Shanghai) XQL-K antistatic agent and 10 parts of sodium stearate.
The preparation method is the same as in example 1.
Example 9
The polyurethane material for the controlled release fertilizer coating comprises the following raw materials in parts by weight: 40 parts of modified castor oil-based polyol II, 40 parts of 4-toluene diisocyanate, 15 parts of straw slag powder liquefier (formed by mixing 50% of straw powder II and 50% of propanol acid), 5 parts of magnesium hydroxide, 5 parts of Hirschiro (Shanghai) XQL-K antistatic agent and 10 parts of sodium stearate.
The preparation method is the same as in example 1.
Example 10
The polyurethane material for the controlled release fertilizer coating comprises the following raw materials in parts by weight: 40 parts of modified castor oil-based polyol II, 40 parts of 4-toluene diisocyanate, 15 parts of straw slag powder liquefier (formed by mixing 50% of straw powder II and 50% of propanol acid), 5 parts of magnesium hydroxide, 5 parts of Hirschiro (Shanghai) XQL-K antistatic agent and 5 parts of sodium stearate.
The preparation method is the same as in example 1.
Comparative example 1
The difference from example 1 is that: no regenerated microcrystals are added to the modified castor oil-based polyol.
Comparative example 2
The difference from example 1 is that: the modified castor oil-based polyol was replaced with the polyester polyol Dynacoll7110.
Comparative example 3
The difference from example 1 is that: no stalk slag powder liquefier is added.
Comparative example 4
The difference from example 1 is that: the liquefied straw slag powder lacks the propionic acid.
Comparative example 5
The difference from example 1 is that: the straw powder liquid in the straw slag powder liquefier accounts for 90 percent and the propanol acid accounts for 10 percent.
Comparative example 6
The difference from example 1 is that: the straw powder liquid in the straw slag powder liquefier accounts for 10 percent and the propanol acid accounts for 90 percent.
Comparative example 7
The difference from example 1 is that: in the preparation raw materials of the straw powder liquid in the straw slag powder liquefier, the mass ratio of the corn straw powder to the PEG600 to the glycerol is 5:2:1.
the polyurethane materials for the controlled release fertilizer coating prepared in each example and comparative example are solidified into a model film, and the mechanical property and weather resistance are tested by the following test method:
(1) Elongation at break: the determination is carried out by referring to the national standard GB/T1701-2001;
(2) Tensile strength: measurements were made with reference to standard ASTM D-412;
(3) Thermal stability: performance testing is performed with reference to SJ/T11475-2014;
(4) Water absorption rate: the water absorption test was performed with reference to GB/T1034-2008.
The measurement results are shown in Table 1:
TABLE 1 polyurethane model film Performance test results for coating of examples and comparative examples controlled release fertilizers
Numbering device Elongation at break (%) Tensile Strength (MPa) Weight change at 120 ℃ (%) Water absorption (%)
Example 1 360 36 3.11 0.23
Example 2 358 36 3.12 0.24
Example 3 356 35 3.14 0.24
Example 4 355 34 3.15 0.25
Example 5 354 33 3.15 0.25
Example 6 354 34 3.16 0.26
Example 7 353 33 3.24 0.26
Example 8 352 32 3.35 0.27
Example 9 350 32 3.38 0.28
Example 10 350 31 3.45 0.28
Comparative example 1 230 20 3.35 0.39
Comparative example 2 325 29 3.38 0.30
Comparative example 3 330 28 4.3 0.29
Comparative example 4 329 29 4.1 0.27
Comparative example 5 330 29 4.0 0.28
Comparative example 6 325 28 3.9 0.29
Comparative example 7 329 28 4.0 0.29
The polyurethane materials for the controlled release fertilizer coating prepared in each example and comparative example are applied to the preparation of the controlled release fertilizer: 10kg of urea with the particle size of 2mm is added into a coating pot, the temperature is raised to 65 ℃, the rotating speed of the coating pot is kept at 30r/min, the coating material of the polyurethane material for coating the controlled release fertilizer of 0.3kg is sprayed onto the surface of urea three times at intervals of 3min each time, talcum powder is added after coating is finished, the obtained product is the controlled release fertilizer, the slow release performance test is carried out on the obtained controlled release fertilizer, the test is carried out according to GB/T23148-2009, and the measurement results are shown in Table 2.
Table 2 cumulative release rate test results for controlled release fertilizers
As can be seen from comparison of the test results of comparative examples 1 and 2 and example 1, the polyurethane material for the controlled release fertilizer coating prepared in example 1 has the advantages that the tensile strength and the elongation at break of the polyurethane material for the controlled release fertilizer coating are effectively improved, the water absorption is effectively reduced, and the polyurethane material for the controlled release fertilizer coating has good toughness and hydrophobicity by adding regenerated microcrystals; from the test results of example 3, comparative example 4, comparative example 5, comparative example 6, comparative example 7 and example 1, it is known that the weight change at high temperature can be effectively reduced and the thermal stability of the polyurethane material for the controlled release fertilizer coating can be improved by adding the liquefied straw slag powder. According to the test results of the comprehensive comparison of the examples and the comparative examples, the mechanical property and the hydrophobicity of the polyurethane material for the controlled-release fertilizer coating are effectively improved by adding the regenerated microcrystal, meanwhile, the polyurethane material for the controlled-release fertilizer coating prepared by adding the straw slag powder liquefier has good weather resistance at high temperature, the raw materials used in the preparation process are renewable, low in cost and degradable, the technical scheme is resource-saving and environment-friendly, the raw material requirement of the controlled-release fertilizer on the polyurethane foaming material can be met, the controlled-release fertilizer prepared by using the polyurethane material for the controlled-release fertilizer coating provided by the invention has good slow release property, the release speed of the fertilizer is more gentle and even, the release period can be effectively prolonged, the nutrient requirement of the whole growing season of crops with longer growing season can be met, the polyurethane prepared by using the traditional petroleum-based polyester polyol can be replaced, and the defects existing in the application of the prior art are well solved.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement it, but not limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.

Claims (10)

1. The polyurethane material for the controlled release fertilizer coating is characterized by comprising the following raw materials in parts by weight: 40-50 parts of modified castor oil-based polyol, 40-50 parts of isocyanate, 15-20 parts of straw slag powder liquefier, 5-10 parts of flame retardant, 5-10 parts of antistatic agent and 5-10 parts of emulsifier.
2. The polyurethane material for controlled release fertilizer coating according to claim 1, wherein the modified castor oil-based polyol comprises the following raw materials in parts by weight: 10-20 parts of regenerated microcrystal, 20-30 parts of castor oil, 20-30 parts of diethanolamine, 5-10 parts of antioxidant and 1-5 parts of catalyst.
3. The polyurethane material for controlled release fertilizer coating according to claim 2, wherein the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1035, antioxidant 1076, triphenyl phosphite and trisnonylphenyl phosphite; the catalyst is selected from one or more of tetrabutyl titanate, tetraisopropyl titanate, organic tin and organic bismuth; the regenerated microcrystal particle size is 20-40 mu m, the polymerization degree is 60-80, and the preparation method comprises the following steps:
pulverizing herba Salsolae Collinae leaf, decocting in boiling water for 5-10min, filtering to obtain residue, adding 3-5% potassium hydroxide solution to adjust pH to 10-12, filtering, washing the residue to neutrality, adding distilled water to adjust pH to 1-2 with 5-10% hydrochloric acid, heating to 50-70deg.C in water bath, adding absolute ethanol, dehydrating, and leaching at room temperature for 4-5 hr;
drying the filter residue obtained in the step (1) at 45-55 ℃, crushing, sieving with a 70-80 mesh sieve, adding into sulfuric acid with the concentration of 40-60%, treating in a shaking table at 45-55 ℃ for 2-3 hours, centrifuging, washing to neutrality, drying the obtained suspension to constant weight at 40-50 ℃, and crushing into powder;
preparing NaOH/urea mixed aqueous solution, pre-cooling to-10 to-5 ℃, adding the powder obtained in the step (2), continuously stirring, adding absolute ethyl alcohol, stirring for 1-2h, and performing centrifugal separation to obtain a product which is regenerated microcrystal;
wherein the mass of the absolute ethyl alcohol in the step (1) is 2-3 times of that of the residue; the quality of the sulfuric acid in the step (2) is 2-3 times of that of the filter residue; in the step (3), the mass fraction of NaOH in the mixed aqueous solution of NaOH/urea is 3-5%, the mass fraction of urea is 5-10%, the mass of the mixed aqueous solution of NaOH/urea is 10-15 times of the mass of the powder obtained in the step (2), and the mass of absolute ethyl alcohol is 2-3 times of the mass of the powder obtained in the step (2).
4. The polyurethane material for controlled release fertilizer coating according to claim 2, wherein the preparation method of the modified castor oil-based polyol comprises the following steps:
heating and steaming castor oil raw materials, stirring to reduce the temperature, and adding diethanolamine and a catalyst for reaction;
adding regenerated microcrystal and antioxidant into the solution obtained in the step (1), and continuously stirring for 1-2h to obtain a product, namely the modified castor oil-based polyol;
wherein the rotary steaming temperature in the step (1) is 100-120 ℃, the rotary steaming time is 10-12h, and the reaction temperature is 60-80 ℃.
5. The polyurethane material for controlled release fertilizer coating according to claim 1, wherein the liquefied straw slag powder is formed by mixing straw powder liquid and propanol acid, wherein the straw powder liquid accounts for 50-70%, and the propanol acid accounts for 30-50%.
6. The polyurethane material for controlled release fertilizer coating according to claim 5, wherein the preparation method of the straw powder liquid comprises the following steps:
PEG600, concentrated sulfuric acid and glycerin are added into a container, and stirred and mixed uniformly;
adding corn stalk powder into the solution obtained in the step (1), heating to react, and adding alkali to adjust the pH value to be neutral after the reaction is finished, wherein the obtained product is stalk powder liquid.
7. The polyurethane material for controlled release fertilizer coating according to claim 6, wherein the mass ratio of the corn stalk powder, PEG600 and glycerin is 1:2-3:3-5, wherein the mass of the concentrated sulfuric acid is 1-2% of the total mass of the corn stalk powder, the PEG600 and the glycerol, the reaction temperature in the step (2) is 140-160 ℃, and the reaction time is 1-2h.
8. The polyurethane material for controlled release fertilizer coating according to claim 1, wherein the isocyanate is selected from one or more of 4-toluene diisocyanate, 2, 6-toluene diisocyanate, isophorone diisocyanate and p-phenylene diisocyanate; the flame retardant is one or a combination of more of magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, melamine polyphosphate and melamine cyanurate; the antistatic agent is selected from XQL-K antistatic agent of Hill (Shanghai) or LS antistatic agent of Jining Beijia; the emulsifier is selected from one or more of sodium stearate, sodium dodecyl sulfate, sorbitan monooleate, polysorbate methylcellulose and sodium carboxymethylcellulose.
9. A method for preparing the polyurethane material for controlled release fertilizer coating according to any one of claims 1 to 8, wherein the method for preparing the polyurethane material for controlled release fertilizer coating comprises the following steps:
adding the modified castor oil-based polyol and isocyanate into a container, maintaining the temperature at 75-85 ℃, stirring and mixing uniformly, and reacting;
and (3) adding the straw slag powder liquefact, the flame retardant, the antistatic agent and the emulsifier into the solution obtained in the step (1), continuously stirring, and carrying out vacuum defoaming after uniformly mixing to obtain the product, namely the polyurethane material for the controlled release fertilizer coating.
10. The application of the polyurethane material for the controlled release fertilizer coating in the technical field of controlled release fertilizer coating according to any one of claims 1 to 8, wherein the application method of the polyurethane material for the controlled release fertilizer coating in the technical field of controlled release fertilizer coating comprises the following steps:
adding fertilizer into a coating pot, heating to 65-70 ℃, and keeping the rotating speed of the coating pot at 30-35r/min;
spraying a polyurethane material coating material for coating the controlled release fertilizer on the surface of the fertilizer in proportion, and adding talcum powder after coating is finished, wherein the obtained product is the controlled release fertilizer;
wherein the grain diameter of the fertilizer in the step (1) is 2-4.75mm, the spraying process in the step (2) is carried out for 3-4 times at intervals of 3-5min each time, and the mass of the polyurethane material coating material for the controlled release fertilizer coating is 2.1-3% of the mass of the fertilizer.
CN202310002816.7A 2023-01-03 2023-01-03 Polyurethane material for controlled release fertilizer coating and preparation method and application thereof Active CN116640289B (en)

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Publication number Priority date Publication date Assignee Title
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CN103304772A (en) * 2013-06-27 2013-09-18 上海永通化工有限公司 Controlled release fertilizer coated by vegetable oil based polyurethane and preparation method thereof
CN105016874A (en) * 2015-07-15 2015-11-04 北京市农林科学院 Straw liquefied coating liquid and preparation method and application thereof
CN115403763A (en) * 2022-08-26 2022-11-29 山东农业大学 Polycondensation type high molecular weight polyalcohol based on castor oil and straw and application thereof

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CN103304772A (en) * 2013-06-27 2013-09-18 上海永通化工有限公司 Controlled release fertilizer coated by vegetable oil based polyurethane and preparation method thereof
CN105016874A (en) * 2015-07-15 2015-11-04 北京市农林科学院 Straw liquefied coating liquid and preparation method and application thereof
CN115403763A (en) * 2022-08-26 2022-11-29 山东农业大学 Polycondensation type high molecular weight polyalcohol based on castor oil and straw and application thereof

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CN117024206A (en) * 2023-10-10 2023-11-10 山东绿四方生态农业科技有限公司 Preparation process of macroelement water-soluble fertilizer for improving soil
CN117024206B (en) * 2023-10-10 2024-01-30 山东绿四方生态农业科技有限公司 Preparation process of macroelement water-soluble fertilizer for improving soil

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