Liquid phase 1-methylcyclopropene stabilizing slow-release agent for preserving fruits, vegetables and flowers and preparation method thereof

Abstract

The application discloses a kind of liquid phase 1-methylcyclopropene stable slow-release agent for fruit and vegetable flower preservation and its preparation method, mainly by active substance 1-methylcyclopropene and as solvent ionic liquid composition, while containing a small amount of surfactant and stabilizer;Preparation method is first dissolved in ionic liquid with suitable surfactant to prepare the solution containing surface activity 0.5%~8%, then control temperature is at 0~5 ℃, under stirring condition, continuously pass in 1-methylcyclopropene gas, 1-methylcyclopropene gas is dissolved after completion, then stir 3 hours, then stand aging certain time, can obtain liquid phase 1-methylcyclopropene stable slow-release agent, and the content of active component 1-methylcyclopropene is 0.01%~25%.The liquid phase 1-methylcyclopropene slow-release agent product obtained by the application has the characteristics of high content of effective component, long stable slow-release time, and the preparation process is simple and convenient to operate.

Description

TECHNICAL FIELD

[0001] The present application relates to fruit and vegetable preservation technology field, especially to a kind of for fruit and vegetable flower preservation liquid phase 1-methylcyclopropene stable slow-release agent and preparation method thereof. BACKGROUND

[0002] 1-methylcyclopropene (1-MCP) is a highly efficient ethylene inhibitor, which can regulate the expression of fruit and vegetable aging-related genes and enzyme activity by preferentially combining with ethylene receptors in fruit and vegetables, thereby inhibiting the ripening of fruit and vegetables by ethylene, delaying fruit postharvest aging, prolonging fruit storage time, and having certain effects on fruit flavor and postharvest diseases. It is an effective and economical fruit and vegetable preservative.

[0003] However, 1-MCP is gaseous at room temperature and normal pressure, which is not easy to store and transport, greatly limiting its application and promotion. The existing method for preparing 1-methylcyclopropene stabilizing slow-release agent uses cyclodextrin substances with cavities to complex and embed 1-methylcyclopropene, so that it forms a relatively stable solid embedding material. In use, a specific solution is used to release it and contact with fruit and vegetables to achieve the purpose of preservation. However, this solid 1-methylcyclopropene preservative has the problems of low effective content (generally less than 4%) and difficult accurate control of effective component content, which becomes a major obstacle in its application process. SUMMARY

[0004] The present application provides a kind of for fruit and vegetable flower preservation liquid phase 1-methylcyclopropene stable slow-release agent and preparation method thereof.

[0005] The scheme of the present application is:

[0006] A kind of for fruit and vegetable flower preservation liquid phase 1-methylcyclopropene stable slow-release agent, including 1-methylcyclopropene active component, ionic liquid, surfactant and stabilizer;The ionic liquid is mainly quaternary ammonium salt ionic liquid, and the quaternary ammonium salt ionic liquid is one of chloridizing hexadecyl dimethyl benzyl ammonium ionic liquid, chloridizing hexadecyl trimethyl ammonium ionic liquid and amino acid ionic liquid;

[0007] The surfactant is non-ionic surfactant, and the non-ionic surfactant is one or a mixture of more of alkyl alcohol polyoxyethylene ether, polyoxyethylene fatty alcohol ether, Span 80 and Tween 80. Among them, ionic liquid exists as a solvent.

[0008] As a preferred technical solution, the stabilizer is one of sodium carboxymethyl cellulose or sodium hydroxyethyl cellulose.

[0009] As a preferred technical scheme, the mass percentage of the 1-methylcyclopropene active component in the stable slow-release agent is 0.01-25%.

[0010] As a preferred technical scheme, the mass percentage of the surfactant in the stable slow-release agent is 0.5-8%.

[0011] As a preferred technical scheme, the mass percentage of the stabilizer in the stable slow-release agent is 0.2-2%.

[0012] A method for preparing a liquid-phase 1-methylcyclopropene stable slow-release agent for preserving fruits, vegetables and flowers, comprising the following steps:

[0013] 1) dissolving a surfactant in an ionic liquid to configure an ionic liquid solution containing the surfactant, and controlling the temperature of the solution;

[0014] 2) bubbling 1-methylcyclopropene gas into the solution in 1) under stirring to form an ionic liquid solution of 1-methylcyclopropene;

[0015] 3) after the 1-methylcyclopropene gas is completely dissolved, adding a stabilizer to the solution, stirring for a certain time, and forming a liquid-phase 1-methylcyclopropene solution;

[0016] 4) stopping the stirring, and after the liquid-phase 1-methylcyclopropene solution is aged for a certain time at 0-5℃, obtaining a liquid-phase 1-methylcyclopropene slow-release agent.

[0017] As a preferred technical scheme, the reaction temperature of the ionic liquid solution containing the surfactant in 1) is controlled at 0-5℃.

[0018] As a preferred technical scheme, the stirring time after the stabilizer is added in 3) is controlled at 4-12h.

[0019] As a preferred technical scheme, the aging time in 4) is controlled at 12-48h.

[0020] As a preferred technical scheme, 4) further comprises that the obtained liquid-phase 1-methylcyclopropene stable slow-release agent is sealed and stored at low temperature before use; and the storage temperature of the liquid-phase 1-methylcyclopropene stable slow-release agent is controlled at <10℃.

[0021] The application discloses a liquid-phase 1-methylcyclopropene stable slow-release agent for preserving fruits, vegetables and flowers and a preparation method thereof.

[0022] Advantages of the application:

[0023] The liquid-phase 1-methylcyclopropene stable slow-release agent is mainly prepared by uniformly dispersing and dissolving 1-methylcyclopropene gas in ionic liquid with the aid of a surfactant, then stabilizing the formed solution with a stabilizer, and finally forming the 1-methylcyclopropene stable slow-release agent.

[0024] The liquid-phase 1-methylcyclopropene stable slow-release agent prepared by the method has a controllable content of the active component 1-methylcyclopropene, a large regulation range, a low-temperature stability, a long slow-release time at a high-temperature environment, and a good preservation effect. DETAILED DESCRIPTION

[0025] The application provides a liquid-phase 1-methylcyclopropene stable slow-release agent for preserving fruits, vegetables and flowers and a preparation method thereof.

[0026] In order to make the technical means, creative features, purposes and effects of the application easy to understand, the application is further described below in combination with specific examples.

[0027] Example 1:

[0028] The liquid-phase 1-methylcyclopropene slow-release agent contains 1-methylcyclopropene as an active component, ionic liquid as a solvent, and a surfactant and a stabilizer.

[0029] 1) The chlorohexadecyldimethylbenzylammonium ionic liquid is added into a reactor, then the polyoxyethylene fatty alcohol ether surfactant is added, and stirring is carried out at 0 DEG C and a rotating speed of 300 rpm for 30 min to form an ionic solution containing 5.56% of the surfactant;

[0030] 2) Add 1-methylcyclopropene equivalent to 10% of the ionic solution containing surfactant into the ionic liquid, seal the container, and stir at a speed of 800 rpm until the 1-methylcyclopropene gas is completely dissolved to form a homogeneous solution;

[0031] 3) Add the stabilizer sodium hydroxyethyl cellulose to the solution of 2), stir for 4 h, and form a liquid 1-methylcyclopropene solution;

[0032] 4) Stop stirring, and allow the solution to stand at 0°C for 24 h to obtain a liquid 1-methylcyclopropene sustained-release preparation with an active component content of 10%. The obtained liquid 1-methylcyclopropene stable sustained-release preparation is stored at a low temperature of 5°C after being sealed and is ready for use.

[0033] Example Two:

[0034] A liquid 1-methylcyclopropene sustained-release preparation containing 1-methylcyclopropene as an active component, ionic liquid as a solvent, and surfactant and stabilizer. The mass ratio of 1-methylcyclopropene, ionic liquid, surfactant, and stabilizer is 25:70:4.9:0.1, and the specific preparation method is as follows:

[0035] 1) Add chlorohexadecyltrimethylammonium ionic liquid and alkyl alcohol polyoxyethylene ether surfactant into a reactor, and stir at 3°C and a speed of 300 rpm for 30 min to form an ionic solution containing 6.67% of surfactant;

[0036] 2) Add 1-methylcyclopropene equivalent to 25% of the ionic solution containing surfactant into the ionic liquid, seal the container, and stir at a speed of 800 rpm until the 1-methylcyclopropene gas is completely dissolved to form a homogeneous solution;

[0037] 3) Add the stabilizer sodium carboxymethyl cellulose to the solution of 2), stir for 7 h, and form a liquid 1-methylcyclopropene solution;

[0038] 4) Stop stirring, and allow the solution to stand at 3°C for 30 h to obtain a liquid 1-methylcyclopropene sustained-release preparation with an active component content of 25%. The obtained liquid 1-methylcyclopropene stable sustained-release preparation is stored at a low temperature of 5°C after being sealed and is ready for use.

[0039] Example Three:

[0040] A liquid 1-methylcyclopropene sustained-release preparation containing 1-methylcyclopropene as an active component, ionic liquid as a solvent, and surfactant and stabilizer. The mass ratio of 1-methylcyclopropene, ionic liquid, surfactant, and stabilizer is 0.1:91:8:0.9, and the specific preparation method is as follows:

[0041] 1) Add hexadecyl dimethyl benzyl ammonium chloride ionic liquid to the reactor, then add Span 80 surfactant, and stir at 5°C and 300 rpm for 30 min to form an ionic solution containing 8% surfactant;

[0042] 2) Add 0.1% of 1-methylcyclopropene, equivalent to the amount of the ionic solution containing the surfactant, to the ionic liquid. Seal the container and stir at 800 rpm until the 1-methylcyclopropene gas is completely dissolved to form a homogeneous solution.

[0043] 3) Add sodium carboxymethyl cellulose stabilizer to solution 2) and stir for 12 hours to form a liquid-phase 1-methylcyclopropene solution;

[0044] 4) Stop stirring and allow the solution to age at 5°C for 24 hours to obtain a liquid-phase 1-methylcyclopropene sustained-release agent with an active component content of 0.1%. The obtained liquid-phase 1-methylcyclopropene stabilized sustained-release agent is sealed and stored at 5°C for later use.

[0045] Example 4:

[0046] A liquid-phase 1-methylcyclopropene sustained-release agent is prepared using 1-methylcyclopropene as the active component, an ionic liquid as the solvent, and containing a surfactant and a stabilizer. The mass ratio of 1-methylcyclopropene, ionic liquid, surfactant, and stabilizer is 15:82.5:0.5:2. The specific preparation method is as follows:

[0047] 1) Add hexadecyl dimethyl benzyl ammonium chloride ionic liquid to the reactor, then add Tween 80 surfactant, and stir at 0℃ and 300 rpm for 30 min to form an ionic solution containing 0.6% surfactant;

[0048] 2) Add 15% of the 1-methylcyclopropene, equivalent to the ionic solution containing the surfactant, to the ionic liquid. Seal the container and stir at 1000 rpm until the 1-methylcyclopropene gas is completely dissolved to form a homogeneous solution.

[0049] 3) Add the stabilizer sodium hydroxyethyl cellulose to the solution in 2) and stir for 12 h to form a liquid-phase 1-methylcyclopropene solution;

[0050] 4) Stop stirring and allow the solution to age at 0℃ for 48 hours to obtain a liquid-phase 1-methylcyclopropene sustained-release agent with an active component content of 15%. The obtained liquid-phase 1-methylcyclopropene stabilized sustained-release agent is sealed and stored at 5℃ for later use.

[0051] 1.0 g of the liquid 1-methylcyclopropene sustained-release agent obtained in Examples 1, 2, 3, and 4 were placed in 100 mL glass bottles, sealed with silicone caps, and the release rate of the active component 1-methylcyclopropene at different storage times at 5°C was tested using gas chromatography. Specific data are shown in Table 1.

[0052] Table 1

[0053]

[0054] As can be seen from the data in Table 1, the liquid-phase 1-methylcyclopropene sustained-release agent obtained by the present invention exhibits good stability at 5°C. Even after being stored for 120 days, the active component 1-methylcyclopropene is released and lost by less than 2%.

[0055] Take 1.0g of the liquid 1-methylcyclopropene sustained-release agent obtained in Examples 1, 2, 3 and 4 respectively and place it in a 100mL glass bottle. Seal with a silicone cap. Use gas chromatography to test the 1-methylcyclopropene release rate of the four products after storage at 10℃, 15℃, 20℃, 25℃, 30℃ and 35℃ for 5 days respectively. The specific data are shown in Table 2.

[0056] Table 2

[0057]

[0058] As shown in Table 2, the release rate of the 1-methylcyclopropene sustained-release agent obtained in this invention increases with increasing temperature. After 5 days of storage at 10℃, the release rate of the active component 1-methylcyclopropene in all four samples did not exceed 10%. After 5 days of storage at 30℃, the release rate of the active component 1-methylcyclopropene in all four samples was approximately 90%. Only when the temperature was further increased to 35℃ and stored for 5 days did the active component 1-methylcyclopropene in all four samples almost completely release. This indicates that the liquid-phase 1-methylcyclopropene sustained-release agent obtained in this invention exhibits a certain slow release process even at relatively high temperatures, which is beneficial for its long-term preservation of fruits and vegetables.

[0059] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A liquid-phase 1-methylcyclopropene stabilizer for preserving fruits, vegetables, and flowers, characterized in that: It includes a 1-methylcyclopropene active component, an ionic liquid, a surfactant, and a stabilizer; the ionic liquid is a quaternary ammonium salt ionic liquid, which is one of hexadecyl dimethyl benzyl ammonium chloride ionic liquid, hexadecyl trimethyl ammonium chloride ionic liquid, and an amino acid ionic liquid; The surfactant is a nonionic surfactant, which is one or more of alkyl alcohol polyoxyethylene ether, polyoxyethylene fatty alcohol ether, Span 80, and Tween 80. The 1-methylcyclopropene active component accounts for 0.01–25% by mass in the stabilized sustained-release agent; The preparation method of the liquid-phase 1-methylcyclopropene stabilized slow-release agent for preserving fruits, vegetables and flowers includes the following steps: 1) Dissolve the surfactant in the ionic liquid to prepare an ionic liquid solution containing the surfactant, and control the temperature of the solution; 2) Under stirring conditions, 1-methylcyclopropene gas is introduced into the solution in 1) to form an ionic liquid solution of 1-methylcyclopropene; 3) After the 1-methylcyclopropene gas is completely dissolved, a stabilizer is added to the solution and stirred for a certain period of time to form a liquid 1-methylcyclopropene solution; 4) Stop stirring and let the liquid-phase 1-methylcyclopropene solution age at 0-5℃ for a certain period of time to obtain the liquid-phase 1-methylcyclopropene sustained-release agent.

2. The liquid-phase 1-methylcyclopropene stabilizer for preserving fruits, vegetables, and flowers as described in claim 1, characterized in that: The stabilizer is either sodium carboxymethyl cellulose or sodium hydroxyethyl cellulose.

3. The liquid-phase 1-methylcyclopropene stabilizer for preserving fruits, vegetables, and flowers as described in claim 1, characterized in that: The surfactant accounts for 0.5% to 8% of the mass of the stabilizer / release agent.

4. The liquid-phase 1-methylcyclopropene stabilizer for preserving fruits, vegetables, and flowers as described in claim 1, characterized in that: The stabilizer accounts for 0.2% to 2% of the total mass of the sustained-release agent.

5. A liquid-phase 1-methylcyclopropene stabilizer for preserving fruits, vegetables, and flowers as described in claim 1, characterized in that: The reaction temperature of the ionic liquid solution containing the surfactant in step 1) is controlled at 0–5°C.

6. The liquid-phase 1-methylcyclopropene stabilizer for preserving fruits, vegetables, and flowers as described in claim 1, characterized in that: After adding the stabilizer in step 3), the stirring time is controlled at 4 to 12 hours.

7. The liquid-phase 1-methylcyclopropene stabilizer for preserving fruits, vegetables, and flowers as described in claim 1, characterized in that: The aging time in 4) is controlled between 12 and 48 hours.

8. The liquid-phase 1-methylcyclopropene stabilizer for preserving fruits, vegetables, and flowers as described in claim 1, characterized in that: The 4) also includes sealing the obtained liquid-phase 1-methylcyclopropene stabilized slow-release agent and storing it at low temperature for later use; the storage temperature of the liquid-phase 1-methylcyclopropene stabilized slow-release agent is controlled at <10℃.

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