Preparation method of epoxidized soybean oil with high epoxy value

Abstract

The invention is suitable for the technical field of epoxidized soybean oil production, and provides a preparation method of high-epoxy-value epoxidized soybean oil, which comprises the following steps: S1, pretreatment: selecting a soybean variety with high oil content to prepare soybean oil, and then carrying out dehydration and deacidification treatment; s2, primary epoxidation reaction: adding the dehydrated and deacidified soybean oil into a reaction container, adding formic acid as a catalyst, then adding hydrogen peroxide, carrying out a reaction, after the reaction is finished, neutralizing the pH value to be neutral, and carrying out liquid separation treatment with water; and S3, secondary epoxidation reaction: continuously adding hydrogen peroxide into the solution in S2, reacting, neutralizing the pH to be neutral after the reaction is finished, separating liquid with water, and then performing rotary evaporation. Through two-side epoxidation treatment, the epoxy value of the epoxidized soybean oil is remarkably increased, and the prepared epoxidized soybean oil is stable in performance, excellent in heat resistance, chemical resistance and durability and wide in application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of epoxy soybean oil production, in particular to a method for preparing high-epoxy value epoxy soybean oil. Background Art

[0002] Epoxidized Soybean Oil (ESO) is a plant-based chemical made from soybean oil by epoxidation. It is widely used in many industries, mainly as a plasticizer, stabilizer and preservative. Epoxidized soybean oil is usually prepared by reacting soybean oil with hydrogen peroxide and a catalyst to oxidize the double bonds in it into epoxy groups.

[0003] The epoxy value refers to the content of epoxy groups (-COC-) in the epoxy soybean oil, usually measured in grams of epoxy groups per 100 grams of the substance. It directly affects the reactivity, physical and chemical properties and performance of the final application of the epoxy soybean oil. Epoxidized soybean oil with a higher epoxy value contains more epoxy groups, so it is more chemically reactive. This makes it easier to cross-link when reacting with chemicals such as hardeners, acids, amines, isocyanates, etc., thereby forming a more stable network structure. This property gives epoxy soybean oil better plasticizing, hardening and cross-linking effects in the production of coatings, adhesives, composites and plastics. Epoxidized soybean oil with a lower epoxy value has weaker reactivity and is suitable for applications that do not require high cross-linking, such as certain types of plastics or paints. It can play a plasticizing or lubricating role, but has less cross-linking reaction.

[0004] Epoxidized soybean oil with high epoxy value is suitable for fields that require strong reactivity and cross-linking effect, and can provide better heat resistance, chemical resistance and durability. Epoxidized soybean oil with low epoxy value is more suitable for applications with high requirements for flexibility and fluidity, such as plasticizers and lubricants. By adjusting the epoxy value, its performance can be optimized according to different needs.

[0005] Most of the existing epoxidized soybean oils have low epoxide values ​​and cannot meet the use requirements in fields requiring strong reactivity and crosslinking effects. Therefore, the present invention provides a method for preparing epoxidized soybean oil with high epoxide value. Summary of the invention

[0006] The present invention aims to provide a method for preparing high-epoxy value epoxidized soybean oil, so as to solve the problem that most of the epoxidized soybean oils in the prior art have low epoxide values ​​and cannot meet the use requirements in fields requiring strong reactivity and crosslinking effect.

[0007] To achieve the above object, the present invention provides the following technical solution: a method for preparing high-epoxy value epoxidized soybean oil, comprising the following steps:

[0008] S1, preprocessing:

[0009] Select soybean varieties with high oil content to obtain soybean oil, and then perform dehydration and deacidification treatment;

[0010] S2, initial epoxidation reaction:

[0011] The dehydrated and deacidified soybean oil is added into a reaction container, and formic acid is added as a catalyst, and then hydrogen peroxide is added to react. After the reaction is completed, the pH is neutralized to neutral, and the soybean oil is treated with water;

[0012] S3, secondary epoxidation reaction:

[0013] Hydrogen peroxide is continuously added to the solution in S2 to carry out the reaction. After the reaction is completed, the pH is neutralized to neutral, the solution is divided with water, and then rotary evaporated.

[0014] Preferably, the soybean oil is dehydrated by heating, and the soybean oil is heated to 100° C. until the moisture content of the soybean oil is less than 0.1%.

[0015] Preferably, the soybean oil deacidification treatment uses sodium hydroxide to neutralize free fatty acids in the soybean oil.

[0016] Preferably, the amount of formic acid in S2 is 0.5-1.5% of the mass of soybean oil.

[0017] Preferably, the concentration ratio of hydrogen peroxide to soybean oil in S2 and S3 is 1:1.

[0018] Preferably, the reaction temperature in S2 is 55-65° C. and the reaction time is 3-4 h.

[0019] Preferably, the reaction temperature in S3 is 60-70° C., and the reaction time is 1-2 h.

[0020] The present invention has at least the following beneficial effects:

[0021] The invention provides a method for preparing high-epoxy value epoxy soybean oil. The epoxy value of the epoxy soybean oil is significantly improved through double-sided epoxidation treatment. The prepared epoxy soybean oil has stable performance, excellent heat resistance, chemical resistance and durability, and has broad application prospects. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] The present invention provides a method for preparing high-epoxy value epoxidized soybean oil, comprising the following steps:

[0024] S1, preprocessing:

[0025] Select soybean varieties with high oil content to obtain soybean oil, and then perform dehydration and deacidification treatment;

[0026] S2, initial epoxidation reaction:

[0027] The dehydrated and deacidified soybean oil is added into a reaction container, and formic acid is added as a catalyst, and then hydrogen peroxide is added to react. After the reaction is completed, the pH is neutralized to neutral, and the soybean oil is treated with water;

[0028] S3, secondary epoxidation reaction:

[0029] Hydrogen peroxide is continuously added to the solution in S2 to carry out the reaction. After the reaction is completed, the pH is neutralized to neutral, the solution is divided with water, and then rotary evaporated.

[0030] Furthermore, the soybean oil is dehydrated by heating the soybean oil to 100° C. until the water content of the soybean oil is less than 0.1%.

[0031] Furthermore, the soybean oil deacidification treatment uses sodium hydroxide to neutralize the free fatty acids in the soybean oil.

[0032] Furthermore, the amount of formic acid in S2 is 0.5-1.5% of the mass of soybean oil.

[0033] Furthermore, the concentration ratio of hydrogen peroxide to soybean oil in S2 and S3 was 1:1.

[0034] Furthermore, the reaction temperature in S2 is 55-65°C, and the reaction time is 3-4h.

[0035] Furthermore, in S3, the reaction temperature is 60-70° C., and the reaction time is 1-2 h.

[0036] The present invention adopts two-step epoxidation reaction, and through the combination of the primary epoxidation reaction and the secondary epoxidation reaction, the double bonds in the soybean oil are fully converted into epoxy groups, thereby increasing the epoxide value of the epoxidized soybean oil. At the same time, by accurately controlling the reaction conditions, such as temperature, time and the amount of catalyst, the high efficiency of the reaction and the stability of the product are ensured.

[0037] The present invention firstly performs a primary epoxidation reaction on the pretreated soybean oil, adds an appropriate amount of formic acid as a catalyst and hydrogen peroxide to react, and controls the reaction temperature and reaction time to ensure that the double bonds in the soybean oil are partially converted into epoxy groups. After the reaction is completed, the byproducts and unreacted raw materials generated by the reaction can be effectively removed by neutralizing the pH to neutral and treating the liquid with water, so as to prepare for the next reaction.

[0038] On the basis of the primary epoxidation reaction, a secondary epoxidation reaction is continued, and the remaining double bonds are further converted into epoxy groups by adding hydrogen peroxide again. Similarly, this step also requires strict control of the reaction conditions and the amount of catalyst to ensure the high efficiency of the reaction and the stability of the product. After the reaction is completed, neutralization, water liquid and rotary evaporation are also carried out to obtain the final high epoxy value epoxidized soybean oil product.

[0039] The preparation method of the present invention can obtain an epoxy soybean oil product with high epoxy value and stable performance, which can meet the market demand for high epoxy value epoxy soybean oil and has broad application prospects. In addition, the method of the present invention is simple and easy to implement, suitable for industrial production, and can meet the market demand for high epoxy value epoxy soybean oil.

[0040] Based on the above technical solution, the present invention provides the following partial embodiments:

[0041] Example 1

[0042] This embodiment provides a method for preparing high-epoxy value epoxidized soybean oil, comprising the following steps:

[0043] S1, preprocessing:

[0044] Selecting soybean varieties with high oil content to obtain soybean oil, heating the soybean oil to 100° C. to dehydrate it until the moisture content in the soybean oil is less than 0.1%, and then using sodium hydroxide to neutralize free fatty acids in the soybean oil;

[0045] S2, initial epoxidation reaction:

[0046] The dehydrated and deacidified soybean oil is added to a reaction container, and formic acid is added as a catalyst, the amount of formic acid is 0.5% of the mass of the soybean oil, and then hydrogen peroxide is added, the concentration ratio of hydrogen peroxide to soybean oil is 1:1, and the reaction is carried out at a reaction temperature of 55° C. and a reaction time of 4 hours. After the reaction is completed, the pH is neutralized to neutral, and the mixture is treated with water;

[0047] S3, secondary epoxidation reaction:

[0048] Continue to add hydrogen peroxide to the solution in S2, the concentration ratio of hydrogen peroxide to soybean oil is 1:1, and react at 60°C for 2 hours. After the reaction, neutralize the pH to neutral, divide the solution with water, and then rotary evaporate.

[0049] Example 2

[0050] This embodiment provides a method for preparing high-epoxy value epoxidized soybean oil, comprising the following steps:

[0051] S1, preprocessing:

[0052] Selecting soybean varieties with high oil content to obtain soybean oil, heating the soybean oil to 100° C. to dehydrate it until the moisture content in the soybean oil is less than 0.1%, and then using sodium hydroxide to neutralize free fatty acids in the soybean oil;

[0053] S2, initial epoxidation reaction:

[0054] The dehydrated and deacidified soybean oil is added to a reaction container, and formic acid is added as a catalyst, the amount of formic acid is 1% of the mass of the soybean oil, and then hydrogen peroxide is added, the concentration ratio of hydrogen peroxide to soybean oil is 1:1, and the reaction is carried out at a reaction temperature of 60° C. and a reaction time of 3.5 hours. After the reaction is completed, the pH is neutralized to neutral, and the mixture is treated with water;

[0055] S3, secondary epoxidation reaction:

[0056] To the solution in S2, hydrogen peroxide was continuously added, the concentration ratio of hydrogen peroxide to soybean oil was 1:1, and the reaction was carried out at a temperature of 65°C and a reaction time of 1.5 h. After the reaction was completed, the pH was neutralized to neutral, the solution was divided with water, and then rotary evaporated.

[0057] Example 3

[0058] This embodiment provides a method for preparing high-epoxy value epoxidized soybean oil, comprising the following steps:

[0059] S1, preprocessing:

[0060] Selecting soybean varieties with high oil content to obtain soybean oil, heating the soybean oil to 100° C. to dehydrate it until the moisture content in the soybean oil is less than 0.1%, and then using sodium hydroxide to neutralize free fatty acids in the soybean oil;

[0061] S2, initial epoxidation reaction:

[0062] The dehydrated and deacidified soybean oil is added to a reaction container, and formic acid is added as a catalyst, the amount of formic acid is 1.5% of the mass of the soybean oil, and then hydrogen peroxide is added, the concentration ratio of hydrogen peroxide to soybean oil is 1:1, and the reaction is carried out at a reaction temperature of 65°C and a reaction time of 3 hours. After the reaction is completed, the pH is neutralized to neutral, and the mixture is treated with water;

[0063] S3, secondary epoxidation reaction:

[0064] Continue to add hydrogen peroxide to the solution in S2, the concentration ratio of hydrogen peroxide to soybean oil is 1:1, and react at 70°C for 1 hour. After the reaction, neutralize the pH to neutral, divide the solution with water, and then rotary evaporate.

[0065] The epoxy value of the products prepared in the above examples 1-3 was tested, and the results were as follows:

[0066] Epoxy value Example 1 7.15g / 100gESO Example 2 7.21g / 100gESO Example 3 7.27g / 100gESO

[0067] In summary, the present invention. By accurately controlling the reaction conditions and the amount of catalyst used, the epoxide value of the epoxidized soybean oil is successfully improved. Compared with the prior art, the epoxidized soybean oil prepared by the present invention has a significantly improved epoxide value, which fully meets the use requirements in fields requiring strong reactivity and crosslinking effects. At the same time, the method of the present invention is simple to operate, the reaction conditions are mild, easy to control, and suitable for industrial production. In addition, the epoxidized soybean oil prepared by the present invention has stable performance, excellent heat resistance, chemical resistance and durability, and has broad application prospects in the fields of coatings, adhesives, composite materials and plastics.

[0068] The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention. It is obvious to those skilled in the art that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic features of the present invention. Therefore, no matter from which point of view, the embodiments should be regarded as exemplary and non-restrictive. The scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims are included in the present invention.

[0069] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing high-epoxy value epoxidized soybean oil, characterized in that: The following steps are involved: S1, preprocessing: Select soybean varieties with high oil content to obtain soybean oil, and then perform dehydration and deacidification treatment; S2, initial epoxidation reaction: The dehydrated and deacidified soybean oil is added into a reaction container, and formic acid is added as a catalyst, and then hydrogen peroxide is added to react. After the reaction is completed, the pH is neutralized to neutral, and the soybean oil is treated with water; S3, secondary epoxidation reaction: Continue to add hydrogen peroxide to the solution in S2 to carry out the reaction. After the reaction is completed, neutralize the pH to neutral, divide the solution with water, and then rotary evaporate.

2. The method for preparing a high epoxy value epoxidized soybean oil according to claim 1, characterized in that: The soybean oil is dehydrated by heating, and the soybean oil is heated to 100° C. until the water content in the soybean oil is less than 0.1%.

3. The method for preparing a high epoxy value epoxidized soybean oil according to claim 1, characterized in that: The soybean oil deacidification treatment uses sodium hydroxide to neutralize free fatty acids in the soybean oil.

4. The method for preparing a high epoxy value epoxidized soybean oil according to claim 1, characterized in that: The amount of formic acid in S2 is 0.5-1.5% of the mass of soybean oil.

5. The method for preparing a high epoxy value epoxidized soybean oil according to claim 1, characterized in that: The concentration ratio of hydrogen peroxide to soybean oil in S2 and S3 is 1:

1.

6. The method for preparing high epoxy value epoxidized soybean oil according to claim 1, characterized in that: The reaction temperature in S2 is 55-65°C and the reaction time is 3-4h.

7. The method for preparing high epoxy value epoxidized soybean oil according to claim 1, characterized in that: The reaction temperature in S3 is 60-70° C. and the reaction time is 1-2 h.