CN110563513B - Modified coating solution for producing slow release fertilizer - Google Patents
Modified coating solution for producing slow release fertilizer Download PDFInfo
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- CN110563513B CN110563513B CN201911012840.9A CN201911012840A CN110563513B CN 110563513 B CN110563513 B CN 110563513B CN 201911012840 A CN201911012840 A CN 201911012840A CN 110563513 B CN110563513 B CN 110563513B
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
Abstract
The modified coating solution for producing the slow release fertilizer is provided, and comprises a basic solution formed by dissolving polystyrene in ethyl acetate, wherein the mass percentage concentration of the polystyrene in the basic solution is 12-14%; the coating solution prepared from the basic solution with the mass percentage concentration of 12-14% contains dibutyl phthalate (DBP) with the mass percentage concentration of 1-5%, styrene-butadiene-styrene triblock copolymer (SBS resin) with the mass percentage concentration of 0.8-1.2% and damping ester with the mass ratio of 27-81: 1000 to the mass of polystyrene contained in the coating solution. The improvement of the comprehensive performance of the coating material not only reflects in the balanced reduction of the release amount of the fertilizer in unit time, but also can achieve the purpose of effectively improving the utilization rate of the fertilizer; the raw materials are easy to obtain, and the recycling of plastic resources is promoted; the film forming quality is smooth, the oxidation resistance and the wear resistance are excellent, the storage and the transportation are convenient, the cost performance is high, and the popularization is more suitable.
Description
Technical Field
The invention belongs to the technical field of chemical metallurgy slow-release fertilizers, and particularly relates to a slow-release fertilizer which is excellent in slow-release performance and can improve the effective utilization rate of the fertilizer; the modified coating solution for producing the slow release fertilizer promotes the recycling of plastic resources, has smooth and clean formed film, excellent oxidation and wear resistance and high cost performance, and is more suitable for popularization.
Background
The slow release fertilizer is characterized in that a layer of substance is coated on the surface of the fertilizer by a physical or chemical method, the release period of the fertilizer is prolonged by slowing down the release rate of active ingredients, the utilization rate of the fertilizer is improved, and the slow release fertilizer has slow release and long-acting properties. The united states is the first country in the world to research slow-release fertilizers [ see the article published in journal of phosphate fertilizer and compound fertilizer entitled "research progress of slow-release fertilizer coating material" by chen hongkong et al, published in 2016 ], and then the countries in the world have raised the heat tide for researching slow-release fertilizers, and various new products and technologies come out one after another. Wherein, the application of the solution method for producing the slow release fertilizer coating is common. Meanwhile, in the production process of preparing the slow release fertilizer by using the solution method, the concentration ratio of each component of the coating solution becomes a key factor for controlling the performance and quality of the slow release fertilizer. Because the concentration of each component formula of the coating solution not only influences the overall viscosity of the coating solution and influences the mechanical property of the coated slow-release fertilizer, but also plays a decisive factor in the coating hydrophilicity of the coating solution and determines the release rate and the release period of the active ingredients of the slow-release fertilizer. Meanwhile, the problem to be overcome is how to balance the effective release and the high-efficiency utilization rate of nutrient components while improving the slow release performance. Therefore, only by adopting the slow release fertilizer coating solution formula with the optimal concentration ratio, the utilization rate of the coated slow release fertilizer can be effectively improved, the slow release effect of the slow release fertilizer can be improved, the long-acting effect of the slow release fertilizer can be exerted and other key quality factor effects, and the following technical scheme is provided.
Disclosure of Invention
The technical problems solved by the invention are as follows: the slow release fertilizer modified coating solution prepared by adopting the concentration ratio has optimal comprehensive performances such as coating solution viscosity, coating slow release fertilizer mechanical property, contact angle and the like, and has the characteristics of oxidation resistance and contribution to improving the absorption and utilization rate of nutrient components; therefore, the release period of the coated slow-release fertilizer can be effectively prolonged, the utilization and absorption rate is improved, the coated solution with the concentration ratio can be used for recycling plastic garbage and applying the plastic garbage to the production of the coated solution, the resource is saved, the environment is protected, the production cost of the coated solution is controlled, the universality on the soil in different regions is excellent, and the coated slow-release fertilizer is more economical and practical and is more suitable for popularization.
The technical scheme adopted by the invention is as follows: the modified coating solution for producing the slow release fertilizer comprises a basic solution, wherein the basic solution is formed by dissolving polystyrene in ethyl acetate, and the mass percentage concentration of the polystyrene in the basic solution is 12-14%; the coating solution prepared from the basic solution with the mass percentage concentration of 12-14% contains dibutyl phthalate (DBP) with the mass percentage concentration of 1-5%, styrene-butadiene-styrene triblock copolymer (SBS resin) with the mass percentage concentration of 0.8-1.2% and damping ester with the mass ratio of 27-81: 1000 to the mass of polystyrene contained in the coating solution.
As a preferable technical scheme, the concentration of the coating basic solution is 12%; the coating solution prepared from the base solution with the mass percentage concentration of 12% contains dibutyl phthalate (DBP) with the mass percentage concentration of 3%, styrene-butadiene-styrene triblock copolymer (SBS resin) with the mass percentage concentration of 1.0% and damping ester with the mass ratio of 54:1000 to the mass of polystyrene contained in the coating solution.
In order to improve the oxidation resistance and the evaporation resistance in the industrial application production of the coating material, meet the low-temperature flow property of universality required by the process application, ensure the compatibility of the coating material and ethyl acetate and comprehensively improve the slow release performance of the coating material, further: the damping ester is mainly prepared by manually blending polybutylene, polysiloxane, silicon dioxide, alkyl succinic acid, adipic acid, metal aluminum salt, iron dioxide and p-hydroxybenzoate.
Compared with the prior art, the invention has the advantages that:
1. according to the scheme, the damping ester prepared by manual blending is used for replacing natural damping grease for adding, firstly, the material is easy to obtain and more economical, and secondly, compared with the addition of natural organic damping grease or mineral oil, the addition of the damping ester prepared by manual blending has excellent flow characteristic and is convenient for film forming; on the other hand, the slow-release fertilizer has excellent anti-oxidation property, and after the slow-release fertilizer is coated, the storage time of the slow-release fertilizer can be effectively prolonged, and the slow-release performance of the slow-release fertilizer (release and control fertilizer) can be correspondingly improved; moreover, the damping ester prepared by manual blending is added, so that the damping ester can be industrially produced in batches compared with the mineral fat active animal fat, and is more easily dissolved in an ethyl acetate solvent compared with the addition of the mineral fat when fully stirred according to the similar compatibility principle; meanwhile, the viscosity-temperature characteristic, higher thermal oxidation stability and lower evaporability of the damping ester are utilized, so that the method is more suitable for the application of the preparation process of the slow release fertilizer by the solution method; moreover, the damping ester prepared by manual blending has lower pour point lubricating property, so that the low-temperature fluidity is excellent, and the preparation requirement of the solution method coated slow-release fertilizer under the lower-temperature condition can be met;
2. the components of the scheme mainly use modified plastics as main raw materials to prepare the coating solution, so that plastic data which is easy to pollute the environment can be recycled, the resource utilization maximization is facilitated, and the environment is protected;
3. the addition of the styrene-butadiene-styrene triblock copolymer with a specific structure can show different mixture characteristics of a single linear polymer, a random copolymer and even a homopolymer, so that the coating solution can be endowed with the characteristics of thermoplastic elastomer and blending compatibility, the bonding force of each component of the coating solution on the molecular interface is effectively modified, the problem of copolymer compatibility and combination is solved, and the stable blending macromolecule compatibilization effect is achieved; by adding the synergistic damping ester and coating the slow release fertilizer with a coating solution prepared at a specific concentration, the coated slow release fertilizer has the effects of higher oil resistance, smoother surface, excellent wear resistance, convenience in storage and transportation, and higher uniformity and attractiveness; meanwhile, the purposes of enhancing more uniform and smooth coating and better slow release effect of the slow release fertilizer coating film are achieved, and the coating film is in accordance with the international (European) standard;
4. in the scheme, the factors of viscosity, mechanical property and contact angle (hydrophilicity) are considered, polystyrene is dissolved in ethyl acetate to form a base solution with the mass percent concentration of 12%, dibutyl phthalate (DBP) with the mass percent concentration of 3% of the total amount of a coating solution, SBS resin (styrene-butadiene-styrene triblock copolymer) with the mass percent concentration of 1.0% of the total amount of the coating solution and damping ester with specific mass are added, the coating solution material formed after full mixing has the best comprehensive performance, the industrial production is facilitated, and the slow release effect of the prepared slow release fertilizer is better;
5. according to the scheme, 12% of polystyrene base solution dissolved in ethyl acetate is selected, ethyl acetate solvent is selected, polystyrene coating is selected, the material is economical and easy to obtain, especially, under the concentration, the change rate of the contact angle in unit time is minimum, and the slow release effect dissolution rate of the coating material measured by a nitrogen water dissolution rate method and a soil leaching method is lower than 40%, so that the national standard is met;
6. according to the scheme, dibutyl phthalate (DBP) with the mass percentage concentration of 3% is used for modifying a base solution by using the characteristic of a plasticizer, SBS resin (styrene-butadiene-styrene triblock copolymer) with the mass percentage concentration of 1.0% is used for realizing urea coating on the base solution by using the characteristic of a reinforcing agent, and the aim of reducing white pollution is fulfilled by adopting an economic means compared with biological coating while the slow release characteristic of the slow release fertilizer is ensured.
Drawings
FIG. 1a is a graph of the effect of base solution mass percent concentration on coating solution viscosity;
FIG. 1b is a graph showing the effect of dibutyl phthalate mass percent concentration on the viscosity of a coating solution;
FIG. 1c is a graph of the effect of SBS resin mass percent concentration on coating solution viscosity;
FIG. 1d is a graph of the effect of damping ester mass percent concentration on the viscosity of the coating solution;
FIG. 2a is a graph of the effect of base solution mass percent concentration on the mechanical properties of the coating solution;
FIG. 2b is a graph showing the effect of dibutyl phthalate mass percentage concentration on the mechanical properties of the coating solution;
FIG. 2c is a chart showing the effect of SBS resin mass percent concentration on the mechanical properties of the coating solution;
FIG. 2d is a graph showing the effect of damping ester mass percent concentration on the mechanical properties of the coating solution;
FIG. 3a is a graph of the effect of base solution mass percent concentration on the hydrophilicity of a coating solution;
FIG. 3b is a graph showing the effect of dibutyl phthalate mass percent concentration on the hydrophilicity of the coating solution;
FIG. 3c is a graph of the effect of SBS resin mass percent concentration on hydrophilicity of the coating solution;
FIG. 3d is a graph of the effect of damping ester mass percent concentration on the hydrophilicity of the coating solution;
FIG. 4a is a graph showing the effect of mass percent concentration of a base solution on the contact angle of a coated slow release fertilizer;
FIG. 4b is a graph showing the influence of dibutyl phthalate mass percentage concentration on the contact angle of the coated slow release fertilizer;
FIG. 4c is a chart showing the effect of SBS resin mass percent concentration on contact angle of the coated slow release fertilizer;
FIG. 4d is a graph showing the effect of damping ester mass percentage concentration on the contact angle of the coated slow release fertilizer;
FIG. 5a is a plan sectional view of the coating material of the present invention under a scanning electron microscope;
FIG. 5b is another sectional view of the coating material of the present invention under a scanning electron microscope;
FIG. 5c is a sectional view of the coating material of the present invention under a scanning electron microscope;
FIG. 5d is another sectional view of the coating material of the present invention under a scanning electron microscope.
Detailed Description
Specific embodiments of the present invention are described below with reference to fig. 1-5. It is to be understood that the following description of the embodiments is merely exemplary and not intended to limit the invention in any way. The experimental methods and the experimental apparatuses in the following examples are conventional methods and conventional apparatuses unless otherwise specified. The test materials used in the following examples are commercially available unless otherwise specified.
The modified coating solution for producing the slow release fertilizer comprises a basic solution, wherein the basic solution is formed by dissolving polystyrene in ethyl acetate, and the mass percentage concentration of the polystyrene in the basic solution is 12-14%; the coating solution prepared from the basic solution with the mass percentage concentration of 12-14% contains dibutyl phthalate (DBP) with the mass percentage concentration of 1-5%, styrene-butadiene-styrene triblock copolymer (SBS resin) with the mass percentage concentration of 0.8-1.2%, and damping ester with the mass ratio of 27-81: 1000 to the mass of polystyrene contained in the coating solution.
Preferably: the concentration of the coating basic solution is 12%; the coating solution prepared from the base solution with the mass percentage concentration of 12 percent contains dibutyl phthalate (DBP) with the mass percentage concentration of 3 percent and styrene-butadiene-styrene triblock copolymer (SBS resin) with the mass percentage concentration of 1.0 percent, and damping ester with the mass ratio of 54:1000 weight to the mass of the polystyrene contained in the coating solution is added.
In order to improve the oxidation resistance and the evaporation resistance in the industrial application production of the coating material, meet the universal low-temperature flow property required by the process application, ensure the compatibility of the coating material and ethyl acetate and comprehensively improve the slow release performance of the coating material, the damping ester is mainly prepared by manually blending polybutylene, polysiloxane, silicon dioxide, alkyl succinic acid, adipic acid, metal aluminum salt, iron dioxide and p-hydroxybenzoate.
Specifically, the method comprises the following steps: polybutylene: particularly, the low-molecular polybutene is used as a thickening agent of the slow release fertilizer to be added, so that the effects of lubrication, adhesion and plasticization are achieved;
polysiloxane: the low-viscosity fluid silicone oil state polysiloxane is selected as the solvent of the slow-release fertilizer damping ester to be added as the main component of the damping ester;
silicon dioxide: the antirust additive is used for antirust addition of the slow release fertilizer; further, the particle size of the silica powder is a nano-scale particle size to increase its performance similar to that of a coated finish rust-preventive wrapping.
Alkyl succinic acid: the slow release fertilizer is used for corrosion prevention and addition of the slow release fertilizer damping ester;
adipic acid: the adipic acid and the silicon dioxide have synergistic effect, and the problems of leakage and volatilization during coating of the liquid phase-change damping ester can be effectively solved by utilizing the microporous capillary force and the interface adsorption effect of the inorganic composite carrier (silicon dioxide), so that the film is formed uniformly. Moreover, when the reaction conditions are that the pH is 5, the reaction temperature is 150 ℃ and the reaction time is 4 hours, the simple physical embedding relationship between the adipic acid and the silicon dioxide can obtain the slow-release fertilizer coating effect with uniform particle size.
Iron dioxide: the iron dioxide is water-soluble acidic oxide, and can react with water and alkali to generate ferrous acid and ferrate; and can be used for the coloring protection of the coating solution.
P-hydroxybenzoic esters: the slow release fertilizer is used for antiseptic and antibacterial addition of the slow release fertilizer damping ester; the effect is superior to that of benzoic acid and sodium salt thereof, and common alcohols are dissolved and then used, and have phenolic hydroxyl structures, so that the antibacterial performance is stronger than that of benzoic acid and sorbic acid. The action mechanism is as follows: destroying the cell membrane of the microorganism, denaturing the protein in the cell, and inhibiting the activities of the respiring enzyme system and the electron transfer enzyme system of the microorganism cell.
Regarding the damping ester mainly prepared by mixing polybutene, polysiloxane, silicon dioxide, alkyl succinic acid, adipic acid, metal aluminum salt, iron dioxide and p-hydroxybenzoate, the mass parts of the components of the known damping ester are respectively as follows: 20-50 parts of polybutene, 5-20 parts of polysiloxane, 2-10 parts of silicon dioxide, 4-7 parts of alkyl succinic acid, 2-3 parts of adipic acid, 5-10 parts of metal aluminum salt, 2-10 parts of iron dioxide and 8-12 parts of p-hydroxybenzoate. The substances can be directly mixed and added into the prepared basic solution and the prepared coating solution, and a finished product of the modified coating solution formula for producing the slow release fertilizer is obtained after full stirring.
In summary, it should be noted that: after the damping ester prepared by manual blending is added into the coating solution, the oxidation resistance of a slow release fertilizer product in the industrial application production of the slow release fertilizer prepared by the coating solution method can be effectively improved, and the evaporation of the coating solution of the slow release fertilizer in application is reduced; meanwhile, the coating solution can improve the low-temperature flow property of the coating solution and meet the universal production requirement of the coating solution in the process production of preparing the slow release fertilizer by using a solution method; meanwhile, the damping ester prepared by manual blending is added, so that the full compatibility with ethyl acetate can be ensured, and the comprehensive slow release performance of the coating material can be improved.
The specific experimental procedure for the present invention proves to be as follows:
first, to investigate the effect of coating solution concentration on membrane performance: 5g of Polystyrene (PS) is weighed, and coating solutions with concentration gradients of 10%, 11%, 12%, 13% and 14% are prepared, and the five groups are combined. 0.27g of damping ester is added; adding dibutyl phthalate (DBP) accounting for 3.0 percent of the total amount of the coating solution for toughening and reinforcing; SBS resin (styrene-butadiene-styrene triblock copolymer) accounting for 1.0% of the total amount of the coating solution is added to improve the tensile strength of the coating material, and then mechanical stirring is carried out to prepare the coating solution for performance test.
To investigate the effect of dibutyl phthalate (DBP) on membrane performance: 5g of Polystyrene (PS) was weighed and prepared into a 12% coating solution. 0.27g of damping ester is added; SBS resin (styrene-butadiene-styrene triblock copolymer) accounting for 1.0 percent of the total amount of the coating solution is added to improve the tensile strength of the coating material; adding dibutyl phthalate (DBP) accounting for 1.0%, 2.0%, 3.0%, 4.0% and 5.0% of the total amount of the coating solution, respectively, to toughen and reinforce. And then mechanically stirring to prepare a coating solution, and performing performance test.
To investigate the effect of SBS resin (styrene-butadiene-styrene triblock copolymer) on film performance: 5g of Polystyrene (PS) was weighed and prepared into a 12% coating solution. 0.27g of damping ester is added; adding dibutyl phthalate (DBP) accounting for 3.0 percent of the total amount of the coating solution, and performing toughening and reinforcing functions; and (3) adding a total of five groups of SBS resin (styrene-butadiene-styrene triblock copolymer) accounting for 0.8%, 0.9%, 1.0%, 1.1% and 1.2% of the total amount of the coating solution to improve the tensile strength of the coating material. And (4) mechanically stirring to prepare a coating solution, and performing performance test.
To study the effect of damping esters on membrane performance: 5g of Polystyrene (PS) was weighed and prepared into a 12% coating solution. Adding dibutyl phthalate (DBP) for toughening and reinforcing; SBS resin (styrene-butadiene-styrene triblock copolymer) accounting for 1.0 percent of the total amount of the coating solution is added to improve the tensile strength of the coating material; 0.27g of damping ester which is 0.5 time, 0.75 time, 1.0 time, 1.25 times and 1.5 times is added into the mixture. And then mechanically stirring, preparing a coating solution contrast experiment, and carrying out performance test.
For the addition of a styrene-butadiene-styrene triblock copolymer of a specific structure, it is to be noted that: the styrene-butadiene-styrene triblock copolymer can show different mixture characteristics of a single linear polymer, a random copolymer and even a homopolymer, so that the coating solution can be endowed with the characteristics of thermoplastic elastomer and blending compatibility, the molecular interface bonding force of each component of the coating solution is effectively modified, the problem of copolymer compatibility and combination is solved, and the stable blending macromolecule solubilization effect is achieved; after the slow release fertilizer is coated by using the coating solution with specific concentration, the coated slow release fertilizer has the effects of higher oil resistance and smoother, tidy and beautiful surface; meanwhile, after the slow release fertilizer is applied, the effects of enhancing more uniform coating, higher smoothness and better slow release effect of the slow release fertilizer coating are achieved, and the coating meets the international (European) standard.
Regarding the european norm: the European Standard Committee sets an evaluation method of the slow/controlled release fertilizer: at 25 ℃, the nutrient release of the slow/controlled release fertilizer needs to meet the following three conditions. Firstly, the release rate of nutrients in the fertilizer is less than 15% in 1 day; ② the nutrient release rate in the fertilizer is less than 75% in 28 days; thirdly, when the identified fertilizer effect period is reached, the release of the fertilizer nutrients is not less than 75 percent.
Considering the factors of viscosity, mechanical property and contact angle (hydrophilicity) of figures 1-4, the invention especially adopts a basic solution with the mass percentage concentration of 12 percent formed by dissolving polystyrene in ethyl acetate, dibutyl phthalate (DBP) with the mass percentage concentration of 3 percent of the total amount of the coating solution, SBS resin (styrene-butadiene-styrene triblock copolymer) with the mass percentage concentration of 1.0 percent of the total amount of the coating solution, and damping ester with the mass ratio of 54:1000 weight to the mass of the polystyrene in the coating solution, the coating solution has the best material comprehensive performance, is beneficial to industrial production, and the prepared slow release fertilizer has better slow release effect.
In addition, the coating material is prepared by adopting a 12% polystyrene base solution dissolved in ethyl acetate, selecting an ethyl acetate solvent and selecting a polystyrene coating, and is economical and easy to obtain, particularly, the change rate of the contact angle in unit time is minimum under the concentration, and the slow-release effect dissolution rate of the coating material measured by a nitrogen water dissolution rate method and a soil leaching method is lower than 40%, so that the coating material meets the national standard.
With respect to national standards, it is to be noted that: the national standard for slow release fertilizers (GB/T23348-2009) in China is implemented in 2009, 9 and 1, and has good applicability to slow release fertilizers processed by potassium fertilizers, nitrogen fertilizers, compound fertilizers and the like, and the standard comprises the following steps: firstly, the initial dissolution rate is less than or equal to 15 percent at 25 ℃; ② the accumulative release rate of nutrients in 28 days is less than or equal to 80 percent; thirdly, in the period of releasing the nutrients of the slow release fertilizer, the nutrient which is not released is less than 20 percent [11 ].
Besides, the invention particularly adopts dibutyl phthalate (DBP) with the mass percentage concentration of 3% to modify the base solution by utilizing the characteristic of a plasticizer thereof, and uses SBS resin (styrene-butadiene-styrene triblock copolymer) with the mass percentage concentration of 1.0% to realize urea coating on the base solution by utilizing the characteristic of a reinforcing agent thereof, thereby ensuring the slow release characteristic of the slow release fertilizer and simultaneously achieving the purpose of reducing white pollution by adopting a more economic means compared with biological coating.
For the representation of the various figures of the specification, first: as to the influence of the formula concentration of each component of the coating solution of the invention on the viscosity of the coating solution, the following can be found (see FIGS. 1a to 1 d): (FIG. 1a) as the concentration of the coating solution increases, the viscosity of the solution also increases, the mass percent concentration reaches a peak value at 12%, and the viscosity value gradually becomes stable as the concentration increases; (FIG. 1b) the viscosity of the solution increases linearly with increasing amounts of dibutyl phthalate (DBP); (FIG. 1c) as the amount of SBS resin (styrene-butadiene-styrene triblock copolymer) increased, the viscosity of the solution increased first and then decreased and peaked at 1.0% of the total amount of SBS resin (styrene-butadiene-styrene triblock copolymer); (FIG. 1d) as the amount of the damping ester is increased, the viscosity of the solution is not changed greatly when the mass ratio of the added mass of the damping ester to the mass of the polystyrene contained in the coating solution is 54:1000 and the mass is larger than the mass of the damping ester, which shows that the influence of the damping ester on the viscosity of the solution is small. In the whole view, when the coating solution is 12%, dibutyl phthalate (DBP) is 3%, SBS resin (styrene-butadiene-styrene triblock copolymer) is 1.0%, and damping ester is appropriate, the viscosity of the coating solution is the highest, which is advantageous for industrial production.
Secondly, the influence of the formula concentration of each component of the coating solution of the invention on the mechanical property of the coating solution can be found (see fig. 2a to fig. 2 d): the concentration of the base solution is changed continuously (tested by a single fiber strength tester, not shown in the figure), and strip-shaped standard sample bars are selected for testing, the concentrations of the five groups of 10%, 11%, 12%, 13% and 14% have no yield load, which shows that the change of the concentration has no influence on the yield load. However, when the film to be tested was produced by the flat-plate doctor method, it was found that (fig. 2a) the maximum load per unit thickness increased and then decreased as the concentration varied in the five groups, and the solution concentration was 12% at the lowest value. With the increasing amount of dibutyl phthalate (DBP) (1%, 2%, 3%, 4%, 5% of five groups of concentration), no yield load exists when the concentration of dibutyl phthalate is 1% -4%, but a yield load (not shown in the figure) appears when the concentration of dibutyl phthalate is 5%, which indicates that dibutyl phthalate can not play a good toughening and reinforcing role in the first four groups, and the fifth group plays a certain toughening and reinforcing role in the envelope material; with increasing concentration of dibutyl phthalate, the maximum load per thickness increased first and then decreased, and reached a maximum at a concentration of 3% (fig. 2 b). As the amount of SBS resin (styrene-butadiene-styrene triblock copolymer) increased, none of the 5 groups (0.8%, 0.9%, 1.0%, 1.1%, 1.2%) had a yield load (not shown), indicating that changes in the concentration of SBS resin (styrene-butadiene-styrene triblock copolymer) had no effect on the yield load; the maximum load per unit thickness increased and then decreased, and was the highest at a SBS resin (styrene-butadiene-styrene triblock copolymer) concentration of 1.1% (fig. 2 c). With the increasing of the amount of the damping ester (by taking 5g of polystyrene in the prepared coating solution as reference, 0.27g of damping ester with the mass being 0.5 time that of the coating solution, 0.27g of damping ester with the mass being 0.75 time that of the coating solution, 0.27g of damping ester with the mass being 1.00 time that of the coating solution, 0.27g of damping ester with the mass being 1.25 times that of the coating solution and 0.27g of damping ester with the mass being 1.50 times that of the coating solution are respectively added for testing), no yield load exists (not shown in the figure), which indicates that the change of the concentration of the damping ester has no influence on the yield load; however, as the amount of damping ester increases, the maximum load per unit thickness of the membrane material increases first and then decreases sharply, and reaches a maximum value at a mass of damping ester 1 times that of 0.27 g. Therefore, in view of the whole, when the coating solution is 12%, dibutyl phthalate (DBP) is 5%, SBS resin (styrene-butadiene-styrene triblock copolymer) is 1.0%, and damping ester is 1 time, the mechanical properties of the coating material are good.
Furthermore, the effect of the formula concentration of each component of the coating solution of the present invention on the hydrophilicity of the coating solution can be found (see fig. 3a to 3 d): the test was completed with the assistance of an OSA60 type surface optical analyzer, and the present experiment measured the hydrophilicity of the coating material by measuring the contact angle of the coating material, the change value of the contact angle over a certain period of time, and the average change rate of the contact angle per unit time. Specifically, prepared coating materials of different coating solutions are cut into square small blocks of about 1 cm, 5 blocks are randomly extracted, and contact angles of the small blocks are measured. The effect of the concentration of each component of the coating solution on the hydrophilicity (contact angle) of the coating solution was determined to be: along with the continuous increase of the concentration of the coating solution, the contact angle of the coating material is increased integrally; the change rate of the contact angle in unit time is reduced and then increased, and when the concentration of the coating solution is 12%, the change rate of the contact angle in unit time is the minimum, which indicates that the slow release effect of the coating material is the best at the concentration (figure 3 a); with the continuous increase of the concentration of dibutyl phthalate (DBP), the contact angle of the coating material is sharply increased after the concentration exceeds 3 percent and then becomes gentle; the rate of change of the contact angle in unit time increases first and then decreases, and the rate of change of the contact angle in unit time is the smallest at a dibutyl phthalate (DBP) concentration of 3.0%, which indicates that the slow release effect of the coating material is the best at this concentration (fig. 3 b); with the increasing concentration of SBS resin (styrene-butadiene-styrene triblock copolymer), the contact angle of the coating material is not changed too much, which shows that SBS resin (styrene-butadiene-styrene triblock copolymer) has no great influence on the initial hydrophilicity of the coating material (not shown in the figure); however, the rate of change of the contact angle per unit time decreased and then increased, and the rate of change of the contact angle per unit time was the smallest at a concentration of SBS resin (styrene-butadiene-styrene triblock copolymer) of 1.0%, indicating that the slow release effect of the coating material was the best at this concentration (fig. 3 c); along with the increasing of the damping ester multiple (0.50 time, 0.75 time, 1.00 time, 1.25 time and 1.50 time of the addition of the damping ester with the mass of 0.27 g) as mentioned above, the contact angle of the coating material is in a descending trend as a whole; the rate of change of the contact angle per unit time increases first and then decreases, and when the damping ester multiple is 1, the rate of change of the contact angle per unit time is the smallest, which indicates that the slow release effect of the coating material is the best at this concentration (fig. 3 d). Overall, when the concentration of the base solution of the coating solution is 12%, dibutyl phthalate (DBP) is 3%, SBS resin (styrene-butadiene-styrene triblock copolymer) is 1.0%, and damping ester is 1 time, the coating material has the best overall slow release effect.
The research on the influence of the formula concentration of each component of the coating solution on the contact angle of the slow release fertilizer after coating can find out that (see fig. 4a to 4 d): along with the continuous increase of the concentration of the coating solution, the contact angle of the coating material is increased integrally; the change rate of the contact angle in unit time is firstly reduced and then increased, and when the concentration of the coating solution is 12%, the change rate of the contact angle in unit time is the minimum, which means that the slow release effect of the coating material is the best at the concentration; with the continuous increase of the concentration of dibutyl phthalate (DBP), the contact angle of the coating material is increased and then becomes smooth; the change rate of the contact angle in unit time is increased and then reduced, and when the concentration of dibutyl phthalate (DBP) is 3.0%, the change rate of the contact angle in unit time is minimum, which indicates that the slow release effect of the coating material is best at the concentration; with the increasing concentration of SBS resin (styrene-butadiene-styrene triblock copolymer), the contact angle of the coating material is not changed greatly, which shows that SBS resin (styrene-butadiene-styrene triblock copolymer) has no great influence on the initial hydrophilicity of the coating material; the change rate of the contact angle in unit time is reduced firstly and then increased, and when the concentration of SBS resin (styrene-butadiene-styrene triblock copolymer) is 1.0%, the change rate of the contact angle in unit time is minimum, which means that the slow release effect of the coating material is best at the concentration; along with the increasing of the damping ester times, the contact angle of the coating material is in a descending trend as a whole; the change rate of the contact angle in unit time is increased firstly and then reduced, and when the damping ester multiple is 1 time, the change rate of the contact angle in unit time is minimum, which indicates that the slow release effect of the coating material is best at the concentration. In general, when the coating solution was 12%, dibutyl phthalate (DBP) was 3%, SBS resin (styrene-butadiene-styrene triblock copolymer) was 1.0%, and damping ester was 1 time (when the coating solution contained 5g of polystyrene, damping ester was 1 time by mass of 0.27 g), the slow release effect of the coating material was good.
In summary, the following steps: the following can be found in conjunction with the drawings of the specification, fig. 5a, fig. 5b, fig. 5c, and fig. 5 d: damping ester prepared by adding manual blending is selected and added; the coating material prepared from the prepared coating solution can clearly and intuitively find whether the inside of the coating material is uniform, the size of the inner pore diameter of the film and the distribution condition through scanning by an electron microscope. The coating solution with the formula shown in fig. 5 a-5 d has the advantages of compact formed film, reliable coating quality, smooth surface, excellent uniformity and wear resistance, oxidation resistance, superior comprehensive slow release performance and obvious superiority to similar slow release coating solutions in the market from the aspect of cost performance; meanwhile, a part of bubbles are dispersed in the internal structure of the coating material under the scanning of an electron microscope. According to the rupture mechanism and the diffusion mechanism of the slow release fertilizer, the damping ester prepared by artificial blending is cooperated, and the slow release performance of the film is remarkably improved: the mechanism of the slow release performance is as follows: effectively ensures that the effective components in the slow release fertilizer can cause the surface of the coating material to break from inside to outside along with the self pressure of the soil and the pressure generated by the outside, thereby releasing the nutrients: namely, the slow release of the slow release fertilizer under the diffusion mechanism of an S-shaped curve is met: the slow release process comprises a first-stage lag phase (water vapor continuously enters the slow release fertilizer, nutrients in the fertilizer are continuously dissolved, and the fertilizer hardly releases the nutrients), a second-stage constant release phase (with continuous entry of the water vapor, continuous increase of the internal pressure of the fertilizer to form a saturated solution, and release of the nutrients at a constant speed under the combined action of external pressure), and a third-stage lag phase (with continuous release of the nutrients, after a certain stage is reached, the concentration of the nutrients in the fertilizer starts to be reduced, the pressure starts to be reduced, and the release rate of the nutrients starts to be continuously slowed down until the pressure reaches zero). The slow release mechanism from inside to outside can comprehensively improve the slow release performance of the film material. Particularly, the damping ester prepared by manual blending is used for replacing natural damping grease for adding, and the damping ester prepared by manual blending is firstly easily obtained, so that the damping ester is more economical and practical and is easier to popularize; secondly, compared with the addition of natural organic damping grease or mineral oil, the addition of the ester damping ester prepared by manual blending endows the slow-release fertilizer with excellent oxidation resistance, the storage time of the slow-release fertilizer can be effectively prolonged after the slow-release fertilizer is coated, the wear resistance is obviously improved, the long-time storage and the long-distance transportation after the slow-release fertilizer is prepared are facilitated, and the slow-release performance of the slow-release fertilizer (controlled-release fertilizer) can be improved; moreover, damping ester is selected to be added, and compared with organic fat such as mineral fat, animal and plant fat and the like, the damping ester is more compatible with ethyl acetate solvent when fully stirred according to the similar compatibility principle; meanwhile, the viscosity-temperature characteristic of the damping ester, higher thermal oxidation stability and lower evaporability are utilized, so that the preparation method is more suitable for the application of the preparation process of the slow release fertilizer by the solution method, and is convenient and fast to popularize; in addition, the damping ester prepared by manual blending has a low pour point lubricating property, so that the low-temperature fluidity is excellent, and the preparation requirement of the solution method coated slow-release fertilizer under a low-temperature condition can be met.
Mention may also be made of: the improvement of the comprehensive performance of the coating material not only reflects in the balanced reduction of the release amount of the fertilizer in unit time, but also can achieve the purpose of effectively improving the utilization rate of the fertilizer.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
The above-mentioned embodiments are merely preferred embodiments of the present invention, which are not intended to limit the scope of the present invention, and therefore, all equivalent changes made by the contents of the claims of the present invention should be included in the claims of the present invention.
Claims (1)
1. The modified coating solution for producing the slow release fertilizer is provided with a basic solution and is characterized in that: the base solution is formed by dissolving polystyrene in ethyl acetate, and the mass percentage concentration of the polystyrene in the base solution is 12%; the coating solution prepared by using the basic solution with the mass percentage concentration of 12 percent contains dibutyl phthalate (DBP) with the mass percentage concentration of 3 percent and styrene-butadiene-styrene triblock copolymer (SBS resin) with the mass percentage concentration of 1.0 percent, and damping ester with the mass ratio of 54:1000 weight to the mass of the polystyrene contained in the coating solution is added; the damping ester comprises the following components in parts by weight: 20-50 parts of polybutene, 5-20 parts of polysiloxane, 2-10 parts of silicon dioxide, 4-7 parts of alkyl succinic acid, 2-3 parts of adipic acid, 5-10 parts of metal aluminum salt, 2-10 parts of iron dioxide and 8-12 parts of p-hydroxybenzoate.
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