Synthesis method of glycidyl neodecanoate

Abstract

The invention relates to the technical field of organic synthesis, and provides a synthesis method of glycidyl neodecanoate, which comprises the following steps: S1, by taking neodecanoic acid and epoxy chloropropane as raw materials, carrying out polymerization reaction under the action of a catalyst to obtain an intermediate; s2, carrying out substitution reaction on the intermediate and caustic soda liquid, and carrying out post-treatment to obtain glycidyl neodecanoate; the liquid caustic soda is added in a reverse caustic soda adding manner. According to the technical scheme, the problems that a pipeline is easy to block and the utilization rate of liquid caustic soda is low when glycidyl neodecanoate is synthesized by a two-step method in the prior art are solved.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for synthesizing glycidyl neodecanoate. Background Art

[0002] Glycidyl neodecanoate is widely used in the field of coatings and can be used as a raw material or an auxiliary agent. The synthesis methods of glycidyl neodecanoate include the following: One-step method: In the presence of a catalyst, neodecanoic acid and epichlorohydrin directly react to generate glycidyl neodecanoate. This method is simple to operate, but the reaction conditions are relatively harsh, requiring high temperature and high pressure, and the product yield is low. Two-step method: First, neodecanoic acid and epichlorohydrin are subjected to a ring-opening reaction under the action of a catalyst to generate chlorohydrin neodecanoate, and then a ring-closing reaction is performed to obtain glycidyl neodecanoate. The reaction conditions of this method are relatively mild and the product yield is high, but there are many reaction steps and the operation is relatively complicated.

[0003] Among them, the method of adding alkali once is adopted in the closed-loop reaction of the two-step method. This method is prone to pipeline blockage and the utilization rate of liquid alkali is low. Therefore, a new method for synthesizing neodecanoic acid glycidyl ester is needed to improve the two-step method for preparing neodecanoic acid glycidyl ester to avoid pipeline blockage, improve the utilization rate of liquid alkali, and improve the quality and market competitiveness of the product. Summary of the invention

[0004] The invention provides a method for synthesizing glycidyl neodecanoate, which solves the problems of easy pipeline blockage and low utilization rate of liquid alkali in synthesizing glycidyl neodecanoate by a two-step method in the related art.

[0005] The technical solution of the present invention is as follows: The present invention provides a method for synthesizing glycidyl neodecanoate, comprising the following steps: S1, using neodecanoic acid and epichlorohydrin as raw materials, carrying out polymerization reaction under the action of a catalyst to obtain an intermediate; S2, subjecting the intermediate to a substitution reaction with liquid alkali, and post-processing to obtain glycidyl neodecanoate; The liquid alkali is added in a reverse alkali addition manner.

[0006] As a further technical solution, the reverse alkali addition is achieved using a reverse alkali addition device.

[0007] As a further technical solution, the post-treatment includes standing and dehydration treatment in sequence.

[0008] As a further technical solution, the mass ratio of the neodecanoic acid, epichlorohydrin and liquid alkali is 1.5~2:1:0.2~0.3.

[0009] As a further technical solution, the temperature of the substitution reaction is 65-75° C., and the time of the substitution reaction is 2-3 hours.

[0010] As a further technical solution, the polymerization reaction temperature is 65-75° C., and the polymerization reaction time is 4-5 hours.

[0011] As a further technical solution, the epichlorohydrin is added dropwise at a rate of 0.08-0.11 kg / s.

[0012] As a further technical solution, the catalyst is one or both of tetramethylammonium neodecanoate and tetramethylammonium chloride.

[0013] As a further technical solution, the amount of the catalyst added is 0.1% to 0.2% of the mass of the neodecanoic acid.

[0014] As a further technical solution, the catalyst is a nickel-platinum catalyst; the preparation method of the nickel-platinum catalyst comprises the following steps: A1. Mixing platinum salt, nickel salt and water, adjusting the pH to alkaline, and obtaining a precipitate; A2. Wash the precipitate until it is neutral, dry it, and calcine it to obtain a nickel-platinum catalyst.

[0015] In the present invention, a nickel-platinum catalyst is used in the synthesis of neodecanoic acid glycidyl ester, thereby further improving the purity and yield of the neodecanoic acid glycidyl ester.

[0016] As a further technical solution, the mass ratio of the platinum salt to the nickel salt is 5:1-3.

[0017] In the present invention, a nickel-platinum catalyst is used in the synthesis of neodecanoic acid glycidyl ester, and especially when the mass ratio of platinum salt to nickel salt is 5:1-3, the purity and yield of neodecanoic acid glycidyl ester are further improved.

[0018] As a further technical solution, the platinum salt includes one or both of chloroplatinic acid and potassium chloroplatinate; the nickel salt includes one or both of nickel nitrate and nickel acetate.

[0019] The working principle and beneficial effects of the present invention are: In the present invention, the reverse alkali addition method is adopted in the closed-loop reaction of the two-step method, which can reduce pipeline blockage, and the utilization rate of liquid alkali is high. At the same time, the synthesized neodecanoic acid glycidyl ester also has the characteristics of high purity and high yield. DETAILED DESCRIPTION

[0020] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. 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.

[0021] Example 1 The synthetic method of neodecanoic acid glycidyl ester comprises the following steps: Polymerization reaction: adding neodecanoic acid to the reactor through the neodecanoic acid metering tank, the one-time addition amount is 2291.276kg, using a thermal oil furnace to heat the materials in the reactor to 70°C, and then adding epichlorohydrin dropwise through the epichlorohydrin metering tank, the dropping time is 4 hours, and the pH value of the solution in the reactor is detected at any time during the dropping process. When the pH is <1, stop dropping, the dropping rate is 0.087kg / s, and the one-time addition amount is 1251.543kg. After the dropwise addition is completed, the catalyst tetramethylammonium neodecanoate and tetramethylammonium chloride are added to the reactor in a mass ratio of 1:1, and the one-time addition amount is 3.03kg. Finally, the thermal oil furnace is used for heating, and the temperature in the reactor is controlled to be kept at 70°C for 4 hours to obtain an intermediate; Substitution reaction: The intermediate is heated to 70°C and liquid alkali is added using a reverse alkaline hydrolysis device. The alkaline hydrolysis time is 2 hours. When the chlorine content in the oil layer is less than 100 ppm, it is allowed to stand and dehydrated to obtain neodecanoic acid glycidyl ester. The mass ratio of neodecanoic acid, epichlorohydrin, and liquid alkali is 1.831:1:0.246.

[0022] The final yield of neodecanoic acid glycidyl ester was 92.0%, the purity was 94.1%, and the utilization rate of liquid alkali was 97.0%.

[0023] Example 2 The synthetic method of neodecanoic acid glycidyl ester comprises the following steps: Polymerization reaction: adding neodecanoic acid to the reactor through the neodecanoic acid metering tank, the one-time addition amount is 2291.276kg, using a thermal oil furnace to heat the materials in the reactor to 65°C, and then adding epichlorohydrin dropwise through the epichlorohydrin metering tank, the dropping time is 4 hours, and the pH value of the solution in the reactor is detected at any time during the dropping process. When the pH is <1, stop dropping, the dropping rate is 0.080kg / s, the one-time addition amount is 1145.638kg, and after the dropwise addition is completed, tetramethylammonium chloride is added to the reactor, the one-time addition amount is 2.29kg, and finally the thermal oil furnace is used for heating, and the temperature in the reactor is controlled at 65°C for 5 hours to obtain an intermediate; Substitution reaction: The intermediate is heated to 65°C and liquid alkali is added using a reverse alkaline hydrolysis device. The alkaline hydrolysis time is 3 hours. When the chlorine content in the oil layer is less than 100 ppm, it is allowed to stand and dehydrated to obtain neodecanoic acid glycidyl ester. The mass ratio of neodecanoic acid, epichlorohydrin and liquid alkali is 2:1:0.3.

[0024] The final yield of neodecanoic acid glycidyl ester is 92.6%, the purity is 94.9%, and the utilization rate of liquid alkali is 97.2%.

[0025] Example 3 The synthetic method of neodecanoic acid glycidyl ester comprises the following steps: Polymerization reaction: adding neodecanoic acid to the reactor through the neodecanoic acid metering tank, the one-time addition amount is 2291.276kg, using a thermal oil furnace to heat the materials in the reactor to 75°C, and then adding epichlorohydrin dropwise through the epichlorohydrin metering tank, the dropping time is 4 hours, and the pH value of the solution in the reactor is detected at any time during the dropping process. When the pH is <1, stop dropping, the dropping rate is 0.106kg / s, the one-time addition amount is 1527.517kg, and after the dropwise addition is completed, tetramethylammonium chloride is added to the reactor, the one-time addition amount is 4.58kg, and finally using a thermal oil furnace for heating, the temperature in the reactor is controlled at 75°C for 4 hours to obtain an intermediate; Substitution reaction: The intermediate is heated to 75°C and liquid alkali is added using a reverse alkaline hydrolysis device. The alkaline hydrolysis time is 2 hours. When the chlorine content in the oil layer is less than 100 ppm, it is allowed to stand and dehydrated to obtain neodecanoic acid glycidyl ester. The mass ratio of neodecanoic acid, epichlorohydrin and liquid alkali is 1.5:1:0.2.

[0026] The final yield of neodecanoic acid glycidyl ester was 92.2%, the purity was 95.1%, and the utilization rate of liquid alkali was 97.6%.

[0027] Example 4 The difference between this embodiment and embodiment 1 is that the catalyst is replaced with a nickel-molybdenum catalyst. The preparation method of the nickel-molybdenum catalyst comprises the following steps: A1. Mix molybdenum nitrate, nickel nitrate and water in a mass ratio of 5:4, adjust the pH to 9, and obtain a precipitate; A2. Wash the precipitate until it is neutral, dry it, and calcine it to obtain a nickel-molybdenum catalyst.

[0028] The yield of the finally prepared neodecanoic acid glycidyl ester was 93.0% and the purity was 97.6%.

[0029] Example 5 The difference between this embodiment and embodiment 1 is that the catalyst is replaced with a nickel-platinum catalyst. The preparation method of the nickel-platinum catalyst comprises the following steps: A1. Mix platinum nitrate, nickel nitrate and water in a mass ratio of 5:4, adjust the pH to 9, and obtain a precipitate; A2. Wash the precipitate until it is neutral, dry it, and calcine it to obtain a nickel-platinum catalyst.

[0030] The yield of the finally prepared neodecanoic acid glycidyl ester was 94.7% and the purity was 97.5%.

[0031] Example 6 The difference between this embodiment and embodiment 1 is that the catalyst is replaced with a nickel-platinum catalyst. The preparation method of the nickel-platinum catalyst comprises the following steps: A1. Mix platinum nitrate, nickel nitrate and water in a mass ratio of 10:1, adjust the pH to 9, and obtain a precipitate; A2. Wash the precipitate until it is neutral, dry it, and calcine it to obtain a nickel-platinum catalyst.

[0032] The yield of the finally prepared glycidyl neodecanoate was 94.1% and the purity was 98.0%.

[0033] Example 7 The difference between this embodiment and embodiment 1 is that the catalyst is replaced with a nickel-platinum catalyst. The preparation method of the nickel-platinum catalyst comprises the following steps: A1. Mix platinum nitrate, nickel nitrate and water in a mass ratio of 5:1, adjust the pH to 9, and obtain a precipitate; A2. Wash the precipitate until it is neutral, dry it, and calcine it to obtain a nickel-platinum catalyst.

[0034] The yield of the finally prepared neodecanoic acid glycidyl ester was 96.8% and the purity was 98.4%.

[0035] Example 8 The difference between this embodiment and embodiment 1 is that the catalyst is replaced with a nickel-platinum catalyst. The preparation method of the nickel-platinum catalyst comprises the following steps: A1. Mix platinum nitrate, nickel nitrate and water in a mass ratio of 5:3, adjust the pH to 9, and obtain a precipitate; A2. Wash the precipitate until it is neutral, dry it, and calcine it to obtain a nickel-platinum catalyst.

[0036] The yield of the finally prepared neodecanoic acid glycidyl ester was 97.0% and the purity was 98.9%.

[0037] Example 9 The difference between this embodiment and embodiment 1 is that the catalyst is replaced with a nickel-platinum catalyst. The preparation method of the nickel-platinum catalyst comprises the following steps: A1. Mix platinum nitrate, nickel acetate and water in a mass ratio of 5:3, adjust the pH to 10, and obtain a precipitate; A2. Wash the precipitate until it is neutral, dry it, and calcine it to obtain a nickel-platinum catalyst.

[0038] The yield of the finally prepared neodecanoic acid glycidyl ester was 97.8% and the purity was 98.6%.

[0039] Comparative Example 1 The difference between this comparative example and Example 1 is only in the steps of the synthesis method of neodecanoic acid glycidyl ester, substitution reaction: the intermediate is heated to 70°C and then liquid alkali is added, the alkaline hydrolysis time is 2 hours, and when the chlorine content in the oil layer is detected to be less than 100 ppm, it is allowed to stand and dehydrated to obtain neodecanoic acid glycidyl ester.

[0040] The final yield of neodecanoic acid glycidyl ester was 85.0%, the purity was 89.6%, and the utilization rate of liquid alkali was 90.5%.

[0041] Compared with Comparative Example 1, the utilization rate of liquid alkali of the neodecanoic acid glycidyl ester prepared in Examples 1 to 9 is higher, and the yield and purity are also higher, indicating that the reverse alkali addition method is adopted in the closed-loop reaction of the two-step method, and the utilization rate of liquid alkali is high. The synthesized neodecanoic acid glycidyl ester also has the characteristics of high purity and yield.

[0042] Compared with Example 1 and Example 4, the yield and purity of the neodecanoic acid glycidyl ester prepared in Examples 5 to 9 are higher, indicating that the use of a nickel-platinum catalyst in the synthesis of neodecanoic acid glycidyl ester further improves the purity and yield of the neodecanoic acid glycidyl ester.

[0043] Compared with Examples 5 to 6, the yield and purity of the neodecanoic acid glycidyl ester obtained in Examples 7 to 9 are higher, indicating that the use of a nickel-platinum catalyst in the synthesis of neodecanoic acid glycidyl ester, especially when the mass ratio of the platinum salt to the nickel salt is 5:1 to 3, further improves the purity and yield of the neodecanoic acid glycidyl ester.

[0044] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for synthesizing glycidyl neodecanoate, characterized in that: The following steps are involved: S1, using neodecanoic acid and epichlorohydrin as raw materials, carrying out polymerization reaction under the action of a catalyst to obtain an intermediate; S2, subjecting the intermediate to a substitution reaction with liquid alkali, and post-processing to obtain glycidyl neodecanoate; The liquid alkali is added in a reverse alkali addition manner.

2. The method for synthesizing glycidyl neodecanoate according to claim 1, characterized in that: The post-treatment includes standing and dehydration treatment in sequence.

3. The method for synthesizing glycidyl neodecanoate according to claim 1, characterized in that: The mass ratio of the neodecanoic acid, epichlorohydrin and liquid caustic soda is 1.5-2:1:0.2-0.

3.

4. The method for synthesizing glycidyl neodecanoate according to claim 1, characterized in that: The temperature of the substitution reaction is 65-75° C., and the time of the substitution reaction is 2-3 hours.

5. The method for synthesizing glycidyl neodecanoate according to claim 1, characterized in that: The polymerization reaction temperature is 65-75° C., and the polymerization reaction time is 4-5 hours.

6. The method for synthesizing glycidyl neodecanoate according to claim 1, characterized in that: The epichlorohydrin is added dropwise at a rate of 0.08-0.11 kg / s.

7. The method for synthesizing glycidyl neodecanoate according to claim 1, characterized in that: The catalyst comprises one or both of tetramethylammonium neodecanoate and tetramethylammonium chloride.

8. The method for synthesizing glycidyl neodecanoate according to claim 1, characterized in that: The amount of the catalyst added is 0.1% to 0.2% of the mass of the neodecanoic acid.

9. The method for synthesizing glycidyl neodecanoate according to claim 7, characterized in that: The catalyst is a nickel-platinum catalyst; the preparation method of the nickel-platinum catalyst comprises the following steps: A1. Mixing platinum salt, nickel salt and water, adjusting the pH to alkaline, and obtaining a precipitate; A2. Wash the precipitate until it is neutral, dry it, and calcine it to obtain a nickel-platinum catalyst.

10. The method for synthesizing glycidyl neodecanoate according to claim 9, characterized in that: The mass ratio of the platinum salt to the nickel salt is 5:1-3.