An amaranth microcapsule suspension agent and an interfacial synthesis method thereof

Abstract

The application discloses a kind of amaranth microcapsule suspending agent and its interface synthesis method.The interface polymerization method includes the following steps: oil phase solution is added to aqueous solution, shear emulsification is carried out, to obtain emulsion;Oil phase is the mixed solution of amaranth essential oil, solvent and oil-soluble monomer;The aqueous solution of aqueous solution is the mixed aqueous solution of dispersant, emulsifier and defoaming agent;Emulsion is heated to 50~55 DEG C, and water-soluble monomer after dilution with water is added, and solidification reaction is carried out;After reaction, the pH of system is adjusted to 5~7, thickening agent, antifreeze and preservative are added, and stirring is mixed uniformly to obtain.The amaranth microcapsule suspending agent product prepared by the method has excellent thermal storage stability and low-temperature stability, the stability problem of amaranth is completely solved, and the stability and persistence of amaranth in actual use process are improved, and the amount of amaranth is reduced.

Description

Technical Field

[0001] This invention relates to an amino ester microcapsule suspension and its interfacial synthesis method. Background Technology

[0002] Diethyl aminoethylhexanoate (DA-6) is a broad-spectrum plant growth regulator that increases the content of chlorophyll, protein, and nucleic acids in plants; enhances photosynthetic rate; improves carbon and nitrogen metabolism; strengthens water and fertilizer absorption; and regulates the plant's water balance, thereby improving drought and cold resistance. It is particularly effective for soybeans, root vegetables, tubers, and leafy vegetables. It can also be used as a fertilizer and fungicide synergist, and as an remedy for pesticide damage.

[0003] Amine ester crude oil is a colorless or pale yellow transparent liquid with a boiling point of 87-88℃. It is slightly soluble in water and soluble in organic solvents such as alcohols and benzenes. It is stable in neutral and weakly acidic media. Amine ester citrate is a white or pale yellow flaky crystal that is readily soluble in solvents such as water and alcohols.

[0004] Currently, most products on the market are liquid formulations based on aminoethyl ester citrate, primarily using water and alcohols as solvents. However, aminoethyl esters are unstable in both water and alcohol and are prone to hydrolysis. In recent years, some soluble powder and soluble granule products have emerged. These formulations inevitably generate dust pollution during production and use, posing a health risk to workers. Therefore, there is a need to develop new formulations of aminoethyl esters. Summary of the Invention

[0005] The purpose of this invention is to provide an amino ester microcapsule suspension and its interfacial polymerization method, which improves the stability of amino esters through microencapsulation and solves the shortcomings of existing product quality and production processes.

[0006] The interfacial polymerization method for amino ester microcapsule suspension provided by the present invention includes the following steps:

[0007] S1. Add the oil phase solution to the aqueous phase solution and perform shear emulsification to obtain an emulsion;

[0008] The oil phase is a mixture of amino ester essential oil, solvent and oil-soluble monomer;

[0009] The aqueous solution is a mixed aqueous solution of dispersant, emulsifier and defoamer;

[0010] S2. Heat the emulsion to 50-55°C, add water-soluble monomer diluted with water, and carry out a curing reaction;

[0011] S3. After the curing reaction is completed, adjust the pH of the system to 5-7, add thickener, antifreeze and preservative, and stir to mix evenly to obtain the amino ester microcapsule suspension.

[0012] In step S1 of the method of the present invention, the conditions for shear emulsification are as follows:

[0013] 10,000 to 12,000 rpm, high shear for 5 to 10 minutes.

[0014] In step S2 of the method of the present invention, the curing reaction takes 2 to 3 hours.

[0015] In step S3, the stirring time is 30 to 40 minutes.

[0016] In the method of the present invention, the solvent may be sec-butyl acetate, solvent oil S-150 or ethyl hexanoate, preferably sec-butyl acetate;

[0017] The oil-soluble monomer may be hexamethylene diisocyanate-based polyisocyanate, polymethylene polyphenyl isocyanate, isophorone diisocyanate, sebacate chloride, or adipate chloride;

[0018] The water-soluble monomer may be ethylenediamine, diethylenetriamine, ethylene glycol, or resorcinol.

[0019] In the method of the present invention, the dispersant may be a naphthalene sulfonate anionic dispersant, a polycarboxylate dispersant, or a sodium lignosulfonate dispersant;

[0020] The naphthalene sulfonate anionic dispersant can be Qingyu Chemical SP-2816 or Gutian Chemical SN.

[0021] The polycarboxylate dispersant can be Jieshi Chemical PICO-WG7 or Qingyu Chemical SP-2728.

[0022] The emulsifier may be a fatty alcohol polyoxyethylene ether emulsifier, a block polyether emulsifier, or a phosphate ester emulsifier;

[0023] The fatty alcohol polyoxyethylene ether emulsifier may be AEO-9 or JFC.

[0024] The block polyether emulsifier can be Gutian Chemical D865 or YUS-5050PB.

[0025] The phosphate ester emulsifier may be Jieshi Chemical YUS-FS3000 or Gutian Chemical PE-K.

[0026] The defoamer may be an organosilicon defoamer or a polyether;

[0027] The thickener may be xanthan gum or magnesium aluminum silicate;

[0028] The antifreeze agent may be ethylene glycol or propylene glycol;

[0029] The preservative may be sodium benzoate or isothiazolinone.

[0030] Preferably, in the method of the present invention, the mass ratios of each raw material are as follows:

[0031] 0.1-10 parts of amino ester essential oil; 3-20 parts of solvent; 0.5-3 parts of oil-soluble monomer; 0.1-3 parts of water-soluble monomer; 1-10 parts of dispersant; 0.5-5 parts of emulsifier; 0.1-1 part of defoamer; 0.5-3 parts of thickener; 1-5 parts of antifreeze; 0.1-1 part of preservative; 50-90 parts of water.

[0032] Preferably, in the method of the present invention, the mass ratios of each raw material are as follows:

[0033] 0.1-10 parts of amino ester essential oil; 3-20 parts of solvent; 2-3 parts of polymethylene polyphenyl isocyanate; 1-3 parts of diethylenetriamine; 1-3 parts of sodium lignosulfonate dispersant; 2-4 parts of fatty alcohol polyoxyethylene ether emulsifier; 0.1-1 part of defoamer; 0.5-3 parts of thickener; 1-5 parts of antifreeze; 0.1-1 part of preservative; 50-90 parts of water.

[0034] Preferably, in the method of the present invention, the mass ratios of each raw material are as follows:

[0035] 0.1-10 parts of amino ester essential oil; 3-20 parts of solvent; 2-3 parts of adipic acid chloride; 1-2 parts of resorcinol; 2-5 parts of polycarboxylate dispersant; 2-5 parts of block polyether emulsifier or phosphate ester emulsifier; 0.1-1 part of defoamer; 0.5-3 parts of thickener; 1-5 parts of antifreeze; 0.1-1 part of preservative; 50-90 parts of water.

[0036] More preferably, in the method of the present invention, the mass of each raw material is as follows 1) or 2):

[0037] 1) 10 parts amino acid ester essential oil; 5 parts solvent; 2-3 parts polymethylene polyphenyl isocyanate; 1 part diethylenetriamine; 1-3 parts sodium lignosulfonate dispersant; 2-4 parts fatty alcohol polyoxyethylene ether emulsifier; 0.3 parts defoamer; 1 part thickener; 4 parts antifreeze; 0.3 parts preservative; 70 parts water;

[0038] 2) 10 parts amino ester essential oil; 5 parts solvent; 2-3 parts adipic acid chloride; 1-2 parts resorcinol; 2-5 parts polycarboxylate dispersant; 2-5 parts block polyether emulsifier or phosphate ester emulsifier; 0.3 parts defoamer; 1 part thickener; 4 parts antifreeze; 0.3 parts preservative; 68 parts water.

[0039] The amino ester microcapsule suspension product prepared by the method of this invention exhibits excellent thermal and low-temperature stability, completely resolving the stability issue of amino esters. Furthermore, it improves the stability and duration of action of amino esters in practical use, while reducing the amount of amino esters required. In particular, the preferred solvent, sec-butyl acetate, not only dissolves the oil-soluble monomers but also further enhances the stability of the amino esters. Detailed Implementation

[0040] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0041] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0042] The methods for determining encapsulation efficiency, thermal decomposition rate, and flowability in the following examples are as follows:

[0043] Encapsulation efficiency testing methods:

[0044] Weigh 1g of sample (accurate to 0.0002g), place it in a 100mL centrifuge tube, add 10mL of water and 20mL of xylene, shake thoroughly, then centrifuge. Transfer the upper organic phase to a 100mL volumetric flask using a pipette. Repeat the extraction twice more using the above method. Dilute the organic phase in the volumetric flask to the mark with methanol, shake well, filter, and determine the mass fraction of free active ingredients according to the active ingredient detection method.

[0045] Calculation: Encapsulation rate = (Mass fraction of active ingredient - Free mass fraction) × 100 / Mass fraction of active ingredient. Test method for thermal decomposition rate: According to "Other preparations" in GB / T 19136.

[0046] Liquidity observation: visual assessment.

[0047] Example 1

[0048] By weight: 10 parts amino ester essential oil, 5 parts sec-butyl acetate, 3 parts AEO-9 emulsifier, 2 parts sodium lignosulfonate, 3 parts PM-200 isocyanate, 1 part diethylenetriamine, 0.2 parts xanthan gum, 0.3 parts sodium benzoate, 1 part magnesium aluminum silicate, 4 parts ethylene glycol, 0.3 parts DX-201 defoamer, and 70.2 parts pure water.

[0049] The preparation steps are as follows:

[0050] 1. Mix and stir the amino acid essential oil, sec-butyl acetate and PM-200 evenly to prepare an oil phase solution;

[0051] 2. Add AEO-9, sodium lignosulfonate and DX-201 to pure water, stir evenly, and prepare an aqueous solution.

[0052] 3. Slowly add the oil phase solution from step 1 to the aqueous phase solution from step 2, and use a high-shear emulsifier to shear and emulsify the mixed liquid at a speed of 10,000 rpm until the particle size meets the requirements.

[0053] 4. While stirring, slowly heat the pre-emulsified emulsion to 55°C. While maintaining this temperature, slowly add diethylenetriamine to the emulsion to initiate a curing reaction. Maintain the temperature for 3 hours, then stop the heat treatment.

[0054] 5. After curing, adjust the pH value of the material to 5.0-7.0.

[0055] 6. Add xanthan gum, sodium benzoate, magnesium aluminum silicate and ethylene glycol to the suspension in step 4, stir and mix evenly to obtain the amino ester microcapsule suspension.

[0056] Example 2: Except for 2 parts of AEO-9 emulsifier and 3 parts of sodium lignosulfonate, the rest are the same as in Example 1.

[0057] Example 3: Except for 2.5 parts of AEO-9 emulsifier and 2.5 parts of sodium lignosulfonate, the rest are the same as in Example 1.

[0058] Example 4: Except for 3.5 parts of AEO-9 emulsifier and 1.5 parts of sodium lignosulfonate, the rest are the same as in Example 1.

[0059] Example 5: Except for 4 parts of AEO-9 emulsifier and 1 part of sodium lignosulfonate, the rest are the same as in Example 1.

[0060] Comparative Example 1: Except for the dispersant being 2 parts of polycarboxylate dispersant, the rest is the same as in Example 1.

[0061] Comparative Example 2 was the same as Example 1 except that the emulsifier was 3 parts of D-865 emulsifier.

[0062] Comparative Example 3: Except for the use of 3 parts of hexamethylene diisocyanate-based polyisocyanate for the oil-soluble capsule material, the rest were the same as in Example 1.

[0063] Comparative Example 4: Except for the use of 3 parts adipic acid chloride for the oil-soluble capsule material, the rest were the same as in Example 1.

[0064] Comparative Example 5 was the same as in Example 1, except that 3 parts of isophorone diisocyanate were used for the oil-soluble capsule material.

[0065] Comparative Example 6 is the same as Example 1, except that the heat preservation reaction time is 1 hour.

[0066] Comparative Example 7 was the same as Comparative Example 3, except that the heat preservation reaction time was 1 hour.

[0067] Comparative Example 8 was the same as Comparative Example 4, except that the heat preservation reaction time was 1 hour.

[0068] Comparative Example 9 was the same as Comparative Example 5, except that the heat preservation reaction time was 1 hour.

[0069] Comparative Example 10 was the same as Example 1 except that the solvent was S-150 solvent oil.

[0070] Comparative Example 11 was the same as Example 2 except that the solvent was S-150 solvent oil.

[0071] Comparative Example 12 is the same as Example 3 except that the solvent is S-150 solvent oil.

[0072] The products prepared in each embodiment and comparative example were tested, and the results are shown in Table 1.

[0073] Table 1. Performance of the products prepared in Examples 1-5 and Comparative Examples 1-12

[0074]

[0075]

[0076] The experimental results in Table 1 show that different encapsulation materials exhibit significantly different coating effects on the active ingredients. Furthermore, insufficient curing time also significantly impacts the coating effect and affects the product's physical flowability. Different combinations and ratios of additives also have a certain influence on product specifications.

[0077] Example 6

[0078] By weight: 10 parts amino ester essential oil, 5 parts sec-butyl acetate, 5 parts D-865 emulsifier (Gutian Chemical block polyether), 2 parts WG7 polycarboxylate dispersant (Jieshi Chemical additive), 3 parts adipyl chloride, 1.2 parts resorcinol, 0.2 parts xanthan gum, 0.3 parts sodium benzoate, 1 part magnesium aluminum silicate, 4 parts ethylene glycol, 0.3 parts DX-201 defoamer, and 68 parts pure water.

[0079] The preparation steps are the same as in Example 1.

[0080] Example 7: Except for 2 parts of D-865 emulsifier and 5 parts of WG7 polycarboxylate dispersant, the rest are the same as in Example 6.

[0081] Example 8: Except for 2.5 parts of D-865 emulsifier and 4.5 parts of WG7 polycarboxylate dispersant, the rest are the same as in Example 6.

[0082] Example 9: Except for 3 parts of D-865 emulsifier and 4 parts of WG7 polycarboxylate dispersant, the rest are the same as in Example 6.

[0083] Example 10: Except for 3.5 parts of D-865 emulsifier and 3.5 parts of WG7 polycarboxylate dispersant, the rest are the same as in Example 6.

[0084] Example 11: Except for 4 parts of D-865 emulsifier and 3 parts of WG7 polycarboxylate dispersant, the rest are the same as in Example 6.

[0085] Comparative Example 13: Except for the fact that the emulsifier was 3 parts of AEO-9 emulsifier, the rest was the same as in Example 6.

[0086] Comparative Example 14: Except for the dispersant being 2 parts of sodium lignosulfonate, the rest was the same as in Example 6.

[0087] Comparative Example 15: Except for the solvent being 5 parts of S-150 solvent oil, the rest was the same as in Example 6.

[0088] Comparative Example 16: Except for the solvent being 5 parts of S-150 solvent oil, the rest was the same as in Example 11.

[0089] The products prepared in each embodiment and comparative example were tested, and the results are shown in Table 2.

[0090] Table 2 shows the performance of the products prepared in Examples 6-11 and Comparative Examples 10-11.

[0091] Example 6 97.66 3.57 good Example 7 78.51 9.74 good Example 8 83.72 6.92 good Example 9 88.75 7.03 good Example 10 91.55 5.87 good Example 11 94.27 5.24 good Comparative Example 13 77.21 18.97 viscous Comparative Example 14 63.74 25.32 viscous Comparative Example 15 96.77 5.64 good Comparative Example 16 93.68 6.92 good

[0092] As can be observed from the experimental results in Table 2, microencapsulation of aminoethyl ester technical material can significantly improve the stability of the product and significantly improve the thermal storage stability of the active ingredient, thus solving the problem of instability of aminoethyl ester preparations.

[0093] Example 1 outperformed the other examples. Analysis of the capsule structure showed that Example 1 was more likely to form a network cross-linked structure and had better capsule density, which is consistent with the experimental results.

[0094] The comparison of Examples 1-5 and Examples 6-11 shows that, in terms of excipients, the preferred combination of excipients is more conducive to forming a well-formed capsule shell, ensuring the density of the capsule shell and the effective encapsulation of the active ingredients. This is another key factor in improving product stability.

Claims

1. An interfacial polymerization method for an amino ester microcapsule suspension, comprising the following steps: S1. Add the oil phase solution to the aqueous phase solution and perform shear emulsification to obtain an emulsion; The oil phase solution is a mixture of amino ester essential oil, solvent and oil-soluble monomer; The aqueous solution is a mixed aqueous solution of dispersant, emulsifier and defoamer; S2. Heat the emulsion to 50~55°C, add water-soluble monomer diluted with water, and carry out a curing reaction; In step S2, the curing reaction takes 2-3 hours. S3. After the curing reaction is completed, adjust the pH of the system to 5-7, add thickener, antifreeze and preservative, and mix evenly to obtain the amino ester microcapsule suspension. The solvent is sec-butyl acetate; The raw materials of the amino ester microcapsule suspension are composed of any one of the following: 1) 0.1-10 parts of amino acid ester essential oil; 3-20 parts of solvent; 2-3 parts of oil-soluble monomer polymethylene polyphenyl isocyanate; 1-3 parts of water-soluble monomer diethylenetriamine; 1-2.5 parts of sodium lignosulfonate dispersant; 2.5-4 parts of fatty alcohol polyoxyethylene ether emulsifier; 0.1-1 part of defoamer; 0.5-3 parts of thickener; 1-5 parts of antifreeze; 0.1-1 part of preservative; 50-90 parts of water; 2) 0.1-10 parts of amino acid ester essential oil; 3-20 parts of solvent; 2-3 parts of oil-soluble monomer adipicoyl chloride; 1-2 parts of water-soluble monomer resorcinol; 2-5 parts of polycarboxylate dispersant; 2-5 parts of block polyether emulsifier or phosphate ester emulsifier; 0.1-1 part of defoamer; 0.5-3 parts of thickener; 1-5 parts of antifreeze; 0.1-1 part of preservative; 50-90 parts of water.

2. The interface aggregation method according to claim 1, characterized in that: In step S1, the conditions for shear emulsification are: 10,000~12,000 RPM, high shear for 5~10 minutes.

3. The interface aggregation method according to claim 1 or 2, characterized in that: In step S3, the stirring time is 30-40 minutes.

4. The interface aggregation method according to claim 1, characterized in that: The raw materials of the amino ester microcapsule suspension are composed of the following 1) or 2): 1) 10 parts amino ester essential oil; 5 parts solvent; 2-3 parts oil-soluble monomer polymethylene polyphenyl isocyanate; 1 part water-soluble monomer diethylenetriamine; 1-3 parts sodium lignosulfonate dispersant; 2-4 parts fatty alcohol polyoxyethylene ether emulsifier; 0.3 parts defoamer; 1 part thickener; 4 parts antifreeze; 0.3 parts preservative; 70 parts water; 2) 10 parts amino ester essential oil; 5 parts solvent; 2-3 parts oil-soluble monomer adipicoyl chloride; 1-2 parts water-soluble monomer resorcinol; 2-5 parts polycarboxylate dispersant; 2-5 parts block polyether emulsifier or phosphate ester emulsifier; 0.3 parts defoamer; 1 part thickener; 4 parts antifreeze; 0.3 parts preservative; 68 parts water.

5. The amino ester microcapsule suspension prepared by the method according to any one of claims 1-4.

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