Preparation method of N-oleo-12-hydroxystearic acid amide

Abstract

The invention provides a preparation method of N-oleyl-12-hydroxystearic acid amide, and relates to the technical field of organic synthesis. According to the preparation method of the N-oleyl-12-hydroxystearic acid amide, zirconium phosphate and nano silicon dioxide serve as a composite catalyst to catalyze the amidation reaction of 12-hydroxystearic acid and oleyl primary amine, the synthesis conversion rate of the 12-hydroxystearic acid is larger than 98%, the synthesis conversion rate is high, the acid value and the amine value of the N-oleyl-12-hydroxystearic acid amide are low, and the preparation method of the N-oleyl-12-hydroxystearic acid amide is suitable for industrial production. And the product has high melting point, good color and stable quality. Moreover, the preparation method provided by the invention does not need to use a solvent, does not need to further purify and refine the prepared N-oleo-12-hydroxystearic acid amide, and is low in cost, small in environmental pollution and suitable for industrial production.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis, in particular to a preparation method of N-oleyl-12-hydroxystearic amide. BACKGROUND

[0002] N-oleyl-12-hydroxystearic amide is an important derivative of 12-hydroxystearic acid, has the effects of lubrication, demolding, antistatic, dispersion, anti-adhesion, scratch resistance, etc., can be used in food and pharmaceutical packaging materials, can significantly reduce the melt viscosity and improve the processing fluidity, and has application potential in many fields. The direct reaction of 12-hydroxystearic acid and an oleyl primary amine to synthesize N-oleyl-12-hydroxystearic amide is a simple and easy industrialization method, however, the synthesis conversion rate of 12-hydroxystearic acid in the prior art is ≤95%, and the synthesis conversion rate is still low. SUMMARY

[0003] Therefore, the present application aims to provide a preparation method of N-oleyl-12-hydroxystearic amide, and improve the synthesis conversion rate of 12-hydroxystearic acid.

[0004] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions: The present application provides a preparation method of N-oleyl-12-hydroxystearic amide, comprising the following steps: Mixing 12-hydroxystearic acid, an oleyl primary amine and a composite catalyst to perform an amidation reaction to obtain N-oleyl-12-hydroxystearic amide; The composite catalyst comprises zirconium phosphate and nano-silicon dioxide.

[0005] Preferably, the mass ratio of the 12-hydroxystearic acid and the oleyl primary amine is 1:0.79-0.92.

[0006] Preferably, the mass ratio of the 12-hydroxystearic acid and the composite catalyst is 100:0.6-3.2.

[0007] Preferably, the mass ratio of the zirconium phosphate and the nano-silicon dioxide is 1:3-6.

[0008] Preferably, the temperature of the amidation reaction is 165-185℃, and the time is 3-5h.

[0009] Preferably, the mixing comprises the following steps: Mixing the 12-hydroxystearic acid and the oleyl primary amine to obtain a first mixture; Secondly mixing the first mixture and the composite catalyst.

[0010] Preferably, the first mixed holding temperature is 80-110℃, and the time is 20-60min.

[0011] Preferably, the acid value of the N-oleyl-12-hydroxystearic acid amide is ≤4.0mg KOH / g, the amine value is ≤2.0mg KOH / g, the melting point is 86-90℃, and the color is ≤4.5 Gardner.

[0012] Preferably, the iodine value of the 12-hydroxystearic acid is ≤4.5I2g / 100g, the color is ≤4 Gardner, and the hydroxyl value is ≥152mg KOH / g. The primary amine content of the oleyl primary amine is ≥98wt%, and the color is ≤100HaZen. The purity of the zirconium phosphate is ≥99wt%, the water content is ≤6wt%, and the median particle size is ≤0.6μm. The purity of the nanosilica is ≥99.9wt%, the water content is ≤0.01wt%, the specific surface area is ≥100m 2 / g, and the median particle size is ≤40nm.

[0013] Preferably, after the amidation reaction, the reaction solution obtained from the amidation reaction is filtered while hot, the filtrate is cooled and granulated to obtain the N-oleyl-12-hydroxystearic acid amide.

[0014] The preparation method of the N-oleyl-12-hydroxystearic acid amide provided by the present application uses zirconium phosphate and nanosilica as a composite catalyst to catalyze the amidation reaction of 12-hydroxystearic acid and oleyl primary amine, the conversion rate of 12-hydroxystearic acid synthesis is >98%, the conversion rate is high, the acid value and amine value of the N-oleyl-12-hydroxystearic acid amide are low, the melting point is high, the color is good, and the product quality is stable. Moreover, the preparation method provided by the present application does not need to use a solvent, and the obtained N-oleyl-12-hydroxystearic acid amide does not need to be further purified and refined, the cost is low, the environmental pollution is small, and it is suitable for industrial production. DETAILED DESCRIPTION

[0015] The present application provides a preparation method of N-oleyl-12-hydroxystearic acid amide, comprising the following steps: Mixing 12-hydroxystearic acid, oleyl primary amine and a composite catalyst to perform an amidation reaction to obtain N-oleyl-12-hydroxystearic acid amide; The composite catalyst comprises zirconium phosphate and nanosilica.

[0016] Unless otherwise specified, the materials and equipment used in the present application are commercially available in the art.

[0017] In the present application, the 12-hydroxystearic acid has a 1CAS No. 36377-33-0; the iodine value of the 12-hydroxystearic acid can be ≤4.5 I2g / 100g, also can be ≤3 I2g / 100g, specifically can be 2.5 I2g / 100g, 3 I2g / 100g, 3.5 I2g / 100g, 4 I2g / 100g or 4.5 I2g / 100g; the color of the 12-hydroxystearic acid can be ≤4 Gardner, also can be ≤3.5 Gardner, specifically can be 2 Gardner, 2.5 Gardner, 3 Gardner, 3.5 Gardner or 4 Gardner; the hydroxyl value of the 12-hydroxystearic acid can be ≥152 mg KOH / g, also can be ≥158 mg KOH / g, specifically can be 152 mg KOH / g, 154 mg KOH / g, 156 mg KOH / g, 158 mg KOH / g or 160 mg KOH / g.

[0018] In the present application, the primary amine content of the oleyl primary amine can be ≥98 wt%, also can be ≥99 wt%, specifically can be 98 wt%, 98.5 wt%, 99 wt%, 99.5 wt% or 99.8 wt%. 1 CAS No. 112-90-3; the primary amine content of the oleyl primary amine can be ≥98 wt%, also can be ≥99 wt%, specifically can be 98 wt%, 98.5 wt%, 99 wt%, 99.5 wt% or 99.8 wt%; the color of the oleyl primary amine can be ≤100 HaZen, also can be <30 HaZen, specifically can be 100 HaZen, 80 HaZen, 50 HaZen, 30 HaZen, 25 HaZen or 20 HaZen.

[0019] In the present application, the mass ratio of the 12-hydroxystearic acid and the oleyl primary amine can be 1:0.79~0.92, also can be 1:0.83~0.89, specifically can be 1:0.79, 1:0.83, 1:0.85, 1:0.87, 1:0.89 or 1:0.92.

[0020] In the present application, the primary amine content of the oleyl primary amine can be ≥98 wt%, also can be ≥99 wt%, specifically can be 98 wt%, 98.5 wt%, 99 wt%, 99.5 wt% or 99.8 wt%. 1 CAS No. 13772-29-7; the particle morphology of the zirconium phosphate can be a layered structure powder; the purity of the zirconium phosphate can be ≥99 wt%, specifically can be 99 wt%, 99.3 wt%, 99.5 wt% or 99.8 wt%; the water content of the zirconium phosphate can be ≤6 wt%, specifically can be 2 wt%, 3 wt%, 4 wt%, 5 wt% or 6 wt%; the median particle size (D 50 ) of the zirconium phosphate can be ≤0.6 μm, specifically can be 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm or 0.6 μm.

[0021] In the present application, the primary amine content of the oleyl primary amine can be ≥98 wt%, also can be ≥99 wt%, specifically can be 98 wt%, 98.5 wt%, 99 wt%, 99.5 wt% or 99.8 wt%. 1CAS No. 60676-86-0; the purity of the nano-silica can be ≥ 99.9wt%, which can be specifically 99.9wt%, 99.93wt%, 99.95wt%, 99.98wt% or 99.99wt%; the water content of the nano-silica can be ≤ 0.01wt%, which can be specifically 0.01wt%, 0.008wt%, 0.005wt%, 0.002wt% or 0.001wt%; the specific surface area of the nano-silica can be ≥ 100m 2 / g, which can be specifically 100m 2 / g, 110m 2 / g, 120m 2 / g, 130m 2 / g, 140m 2 / g or 150m 2 / g; the median particle size of the nano-silica can be ≤ 40nm, which can be specifically 10nm, 20nm, 30nm, 35nm or 40nm.

[0022] In the present application, the mass ratio of the zirconium phosphate and the nano-silica can be 1:3~6, and can also be 1:3.5~5.5, which can be specifically 1:3, 1:3.5, 1:3.8, 1:4.2, 1:5.5 or 1:6; the mass ratio of the 12-hydroxystearic acid and the composite catalyst can be 100:0.6~3.2, and can also be 100:1.1~2.6, which can be specifically 100:0.6, 100:1.1, 100:1.2, 100:1.8, 100:2.6 or 100:3.2.

[0023] In the present application, the mixing can include the following steps: first mixing 12-hydroxystearic acid and oil-based primary amine to obtain a first mixture; and second mixing the first mixture and a composite catalyst. In the present application, the first mixing is preceded by preheating; the preheating temperature can be 75-90℃, and can be specifically 75℃, 80℃, 85℃ or 90℃; the first mixing can be specifically stirring mixing; the holding temperature of the first mixing can be 80-110℃, and can also be 85-105℃, and can be specifically 80℃, 85℃, 90℃, 98℃, 105℃ or 110℃; the process of increasing the temperature from the preheating temperature to the holding temperature of the first mixing can be specifically steam heating; and the time of the first mixing can be 20-60min, and can also be 30-40min, and can be specifically 20min, 30min, 35min, 40min, 50min or 60min. In the present application, the 12-hydroxystearic acid is first melted into a liquid by preheating the 12-hydroxystearic acid and the oil-based primary amine, and then the raw materials are mixed uniformly by stirring mixing, and then mixed with the composite catalyst, thereby inhibiting the generation of side reactions and improving the selectivity of N-oleyl-12-hydroxystearic acid amide.

[0024] In the present application, the temperature of the amidation reaction can be 165-185℃, and can also be 168-180℃, and can be specifically 165℃, 168℃, 170℃, 178℃, 180℃ or 185℃; and the time of the amidation reaction can be 3-5h, and can be specifically 3h, 3.5h, 4h, 4.5h or 5h. In the present application, the process of the amidation reaction also includes steamming out the water generated in the amidation reaction from the reaction system (i.e. in the form of water vapor). In the present application, the water generated in the reaction is steammed out, thereby promoting the forward progress of the amidation reaction and improving the synthesis conversion rate of the raw materials and the yield of N-oleyl-12-hydroxystearic acid amide.

[0025] After the amidation reaction is completed, the present application also includes filtering the reaction liquid obtained in the amidation reaction while hot, cooling the filtrate and then granulating to obtain the N-oleyl-12-hydroxystearic acid amide. In the present application, the device used for the filtering can be a precision filter; and the final temperature of the cooling can be 28-35℃, and can be specifically 28℃, 29℃, 30℃, 31℃, 32℃, 33℃, 34℃ or 35℃. The present application does not have special limitations on the parameters of the granulation, and a conventional granulation method of the present application can be used. In the present application, the shape of the N-oleyl-12-hydroxystearic acid amide can be specifically spherical; and the particle size of the N-oleyl-12-hydroxystearic acid amide can be 30-60 mesh, and can be specifically 30 mesh, 40 mesh, 50 mesh or 60 mesh. In the present application, the reaction liquid obtained is cooled and then granulated, thereby making the finished N-oleyl-12-hydroxystearic acid amide easy to use.

[0026] In the present application, the acid value of the N-oleyl-12-hydroxystearic acid amide can be ≤4.0 mg KOH / g, specifically 2.5 mg KOH / g, 2.9 mg KOH / g, 3 mg KOH / g, 3.5 mg KOH / g, 3.9 mg KOH / g or 4 mg KOH / g; the amine value of the N-oleyl-12-hydroxystearic acid amide can be ≤2.0 mg KOH / g, specifically 1.2 mg KOH / g, 1.4 mg KOH / g, 1.6 mg KOH / g, 1.8 mg KOH / g or 2 mg KOH / g; the melting point of the N-oleyl-12-hydroxystearic acid amide can be 86-90℃, specifically 86℃, 87℃, 88℃, 89℃ or 90℃; the color of the N-oleyl-12-hydroxystearic acid amide can be ≤4.5 Gardner, specifically 3 Gardner, 3.5 Gardner, 4 Gardner or 4.5 Gardner.

[0027] In order to further illustrate the present application, the schemes provided by the present application are described in detail below in combination with examples, but they should not be understood as limiting the scope of protection of the present application.

[0028] Example 1 12-hydroxystearic acid and oleyl primary amine were added to the reactor at a mass ratio of 1600:1364, the steam was warmed to 80℃, the stirring was started, the temperature was controlled at 95-98℃ for stirring and mixing for 40 min, then the composite catalyst was added, and the amidation reaction was carried out at 173-178℃ for 4 h, water vapor was distilled off during the reaction, after the reaction was completed, the obtained reaction liquid was filtered with a precision filter while hot, and the filtrate was granulated after cooling to obtain N-oleyl-12-hydroxystearic acid amide. Among them, the mass ratio of 12-hydroxystearic acid and composite catalyst was 100:2.8; the mass ratio of zirconium phosphate and nano silicon dioxide in the composite catalyst was 1:3.8.

[0029] Example 2 12-hydroxystearic acid and oleyl primary amine were added to the reactor at a mass ratio of 1600:1342, the steam was warmed to 85℃, the stirring was started, the temperature was controlled at 92-96℃ for stirring and mixing for 40 min, then the composite catalyst was added, and the amidation reaction was carried out at 170-175℃ for 5 h, water vapor was distilled off during the reaction, after the reaction was completed, the obtained reaction liquid was filtered with a precision filter while hot, and the filtrate was granulated after cooling to obtain N-oleyl-12-hydroxystearic acid amide. Among them, the mass ratio of 12-hydroxystearic acid and composite catalyst was 100:1.5; the mass ratio of zirconium phosphate and nano silicon dioxide in the composite catalyst was 1:4.

[0030] Example 3 The 12-hydroxystearic acid and the oil-based primary amine are added to the reactor in a mass ratio of 1600:1364, the steam is warmed to 75-85℃, the stirring is started, the temperature is controlled at 95-98℃, and the mixture is stirred for 40 min, then the catalyst activated alumina is added, the amidation reaction is carried out at 173-178℃ for 4 h, water vapor is distilled off during the reaction, after the reaction is completed, the obtained reaction liquid is filtered with a precision filter while hot, the filtrate is cooled and granulated to obtain N-octyl-12-hydroxystearic acid amide. Among them, the mass ratio of 12-hydroxystearic acid to catalyst is 1600:32.

[0031] Comparative Example 1 The 12-hydroxystearic acid and the oil-based primary amine are added to the reactor in a mass ratio of 1600:1364, the steam is warmed to 75-85℃, the stirring is started, the temperature is controlled at 95-98℃, and the mixture is stirred for 40 min, then the catalyst activated alumina is added, the amidation reaction is carried out at 173-178℃ for 4 h, water vapor is distilled off during the reaction, after the reaction is completed, the obtained reaction liquid is filtered with a precision filter while hot, the filtrate is cooled and granulated to obtain N-octyl-12-hydroxystearic acid amide. Among them, the mass ratio of 12-hydroxystearic acid to catalyst is 1600:32.

[0032] Comparative Example 2 The 12-hydroxystearic acid and the oil-based primary amine are added to the reactor in a mass ratio of 1600:1364, the steam is warmed to 75-85℃, the stirring is started, the temperature is controlled at 95-98℃, and the mixture is stirred for 40 min, then the catalyst activated alumina is added, the amidation reaction is carried out at 173-178℃ for 4 h, water vapor is distilled off during the reaction, after the reaction is completed, the obtained reaction liquid is filtered with a precision filter while hot, the filtrate is cooled and granulated to obtain N-octyl-12-hydroxystearic acid amide. Among them, the mass ratio of 12-hydroxystearic acid to catalyst is 1600:32.

[0033] Comparative Example 3 The 12-hydroxystearic acid and the oil-based primary amine are added to the reactor in a mass ratio of 1600:1364, the steam is warmed to 75-85℃, the stirring is started, the temperature is controlled at 95-98℃, and the mixture is stirred for 40 min, then the catalyst activated alumina is added, the amidation reaction is carried out at 173-178℃ for 4 h, water vapor is distilled off during the reaction, after the reaction is completed, the obtained reaction liquid is filtered with a precision filter while hot, the filtrate is cooled and granulated to obtain N-octyl-12-hydroxystearic acid amide. Among them, the mass ratio of 12-hydroxystearic acid to catalyst is 1600:32.

[0034] Comparative Example 4 The 12-hydroxystearic acid and the oil-based primary amine are added into a reactor in a mass ratio of 1600:1364, steam is warmed to 75-85 DEG C, stirring is started, the temperature is controlled to 95-98 DEG C, and stirring and mixing are carried out for 40 min, then the catalyst zirconium phosphate is added, amidation reaction is carried out at 173-178 DEG C for 4 h, water vapor is distilled off during the reaction, after the reaction is completed, the obtained reaction liquid is filtered with a precision filter while hot, the filtrate is cooled and granulated, and N-octyl-12-hydroxystearic acid amide is obtained, wherein the mass ratio of the 12-hydroxystearic acid and the catalyst is 1600:12.8.

[0035] Comparative Example 5 The 12-hydroxystearic acid and the oil-based primary amine are added into a reactor in a mass ratio of 1600:1364, steam is warmed to 75-85 DEG C, stirring is started, the temperature is controlled to 95-98 DEG C, and stirring and mixing are carried out for 40 min, then the catalyst nano silicon dioxide is added, amidation reaction is carried out at 173-178 DEG C for 4 h, water vapor is distilled off during the reaction, after the reaction is completed, the obtained reaction liquid is filtered with a precision filter while hot, the filtrate is cooled and granulated, and N-octyl-12-hydroxystearic acid amide is obtained, wherein the mass ratio of the 12-hydroxystearic acid and the catalyst is 1600:33.2.

[0036] The synthetic conversion rates of the 12-hydroxystearic acid and the oil-based primary amine in the Examples 1-3 and the Comparative Examples 1-5 are calculated, the acid value, the amine value, the melting point and the color of the obtained N-octyl-12-hydroxystearic acid amide are tested, and the results are shown in Table 1.

[0037] Table 1 The synthetic conversion rates of the raw materials, the acid value, the amine value, the melting point and the color of the N-octyl-12-hydroxystearic acid amide in the Examples 1-3 and the Comparative Examples 1-5

[0038] Table 1 is the synthetic conversion rates of the raw materials, the acid value, the amine value, the melting point and the color of the N-octyl-12-hydroxystearic acid amide in the Examples 1-3 and the Comparative Examples 1-5. It can be seen from Table 1 that the raw material conversion rate of the preparation method provided by the application is high, the synthetic conversion rate of the 12-hydroxystearic acid is >98%, the synthetic conversion rate of the oil-based primary amine is >99%, the acid value and the amine value of the prepared N-octyl-12-hydroxystearic acid amide are low, the melting point is high, and the color is good.

[0039] The above only describes the preferred embodiments of the present application, and it should be noted that the ordinary skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A process for the preparation of N-oleyl-12-hydroxystearic acid amide, characterized in that, The method comprises the following steps: Mixing 12-hydroxystearic acid, an oil-based primary amine and a composite catalyst to perform an amidation reaction to obtain N-octyl-12-hydroxystearic acid amide. The composite catalyst comprises zirconium phosphate and nano-silica.

2. The production method according to claim 1, characterized by, The mass ratio of the 12-hydroxystearic acid and the oil-based primary amine is 1:0.79-0.

92.

3. The preparation method according to claim 1, characterized in that, The mass ratio of the 12-hydroxystearic acid and the composite catalyst is 100:0.6-3.

2.

4. The method of claim 1, wherein, The mass ratio of the zirconium phosphate and the nano-silica is 1:3-6.

5. The method of any one of claims 1 to 4, wherein the method further comprises the step of: The temperature of the amidation reaction is 165-185℃, and the time is 3-5h.

6. The method of claim 1, wherein, The mixing comprises the following steps: Mixing 12-hydroxystearic acid and an oil-based primary amine to obtain a first mixture; Secondly mixing the first mixture and a composite catalyst.

7. The preparation method according to claim 6, characterized in that, The holding temperature of the first mixing is 80-110℃, and the time is 20-60min.

8. The method of claim 1, wherein, The acid value of the N-octyl-12-hydroxystearic acid amide is ≤4.0mg KOH / g, the amine value is ≤2.0mg KOH / g, the melting point is 86-90℃, and the color is ≤4.5 Gardner.

9. The production method according to claim 1 or 2, characterized by, The iodine value of the 12-hydroxystearic acid is ≤4.5I2g / 100g, the color is ≤4 Gardner, and the hydroxyl value is ≥152mg KOH / g; The primary amine content of the oil-based primary amine is ≥98wt%, and the color is ≤100HaZen; The purity of the zirconium phosphate is ≥99wt%, the water content is ≤6wt%, and the median particle size is ≤0.6μm; The purity of the nano-silica is ≥ 99.9wt%, the water content is ≤ 0.01wt%, the specific surface area is ≥ 100m 2 / g, and the median particle size is ≤ 40nm.

10. The method of claim 1, wherein, After the amidation reaction, the method further comprises filtering the reaction liquid obtained by the amidation reaction while hot, granulating the filtrate after cooling to obtain the N-octyl-12-hydroxystearic acid amide.

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