A synthesis process of a general anti-yellowing ethylene bis-stearamide

Abstract

The application discloses a synthesis process of general anti-yellowing ethylene bis-stearamide, and relates to the technical field of organic chemical synthesis.The application comprises the following steps: step one, replacing the reaction system with nitrogen, and detecting the nitrogen concentration to be more than 99.9%; step two, putting 1000 parts of stearic acid into a reaction kettle, and starting to heat; step three, after the stearic acid is completely melted and the temperature is increased to 80-95 DEG C, 110-150 parts of ethylenediamine is added into the reaction system at a dropping speed of 5.5 parts per minute, and stirring is conducted for 1 hour after the dropping is completed.The application adopts stearic acid as a main raw material to add ethylenediamine for organic synthesis reaction, adopts different catalysts and activators according to different reaction sections and reaction mechanisms, and adds suitable composite antioxidants, so that the general anti-yellowing ethylene bis-stearamide is prepared, and the problem of yellowing of products added with ethylene bis-stearamide can be effectively solved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic chemical synthesis, and particularly relates to a synthesis process of a general anti-yellowing ethylene bis-stearamide. BACKGROUND

[0002] After the vigorous development of the domestic petrochemical industry, ethylene bis-stearamide, as one of the important additives in the plastic industry in the petrochemical industry, has become a key technology for improving the plastic production capacity and performance. At present, domestic high-end plastic products rely on imported ethylene bis-stearamide from abroad.

[0003] Ethylene bis-stearamide contains two amide groups -CO-NH- in its molecular structure, so that various by-products are easily produced in the synthesis reaction, which causes the material to be easily colored in the reaction process, the purity of the finished product to be low, the heat resistance to be poor, and the problem of color change of the product after processing to exist, which is limited in product application.

[0004] Therefore, the synthesis process of the general anti-yellowing ethylene bis-stearamide is provided to meet the demand of high-end plastic products. SUMMARY

[0005] The purpose of the application is to provide a synthesis process of a general anti-yellowing ethylene bis-stearamide to solve the existing problems: ethylene bis-stearamide contains two amide groups -CO-NH- in its molecular structure, so that various by-products are easily produced in the synthesis reaction, which causes the material to be easily colored in the reaction process, the purity of the finished product to be low, the heat resistance to be poor, and the problem of color change of the product after processing to exist, which is limited in product application.

[0006] To solve the above technical problems, the application is realized by the following technical scheme:

[0007] The application is a synthesis process of a general anti-yellowing ethylene bis-stearamide, which comprises the following steps:

[0008] Step one: replace the reaction system with nitrogen, and detect the nitrogen concentration to be more than 99.9%;

[0009] Step two: put 1000 parts of stearic acid into a reaction kettle and start heating;

[0010] Step three: after the stearic acid is completely melted and heated to 80-95 DEG C, 110-150 parts of ethylenediamine are added to the reaction system at a dropping speed of 5.5 parts per minute, and stirring is performed for 1 hour after the dropping is completed;

[0011] Step four: temperature is raised to 175-180℃ at a rate of 0.5℃ / hr, 2-5 parts of composite catalyst is added when the temperature reaches 135℃, and condensed water is continuously collected, when the water output is less than 0.3g / 10min, the temperature is reduced to 160-165℃;

[0012] Step five: 0.5-2 parts of composite antioxidant is added into the material, stirring is continuously conducted for 30min, and rapid cooling is conducted to form a shape.

[0013] Further, the step two further comprises the following steps:

[0014] When the stearic acid is completely melted and the temperature reaches 85℃, 0.3-1 parts of the first-stage composite activator is added, and stirring is conducted for 10min.

[0015] Further, the first-stage composite activator is phosphoric acid, sodium dihydrogen phosphate and p-toluenesulfonic acid mixed uniformly at a molar ratio of 1:0.3:0.3.

[0016] Further, the composite catalyst in the step four is 4-dimethylaminopyridine, phosphorous acid and boric acid mixed uniformly at a molar ratio of 1:0.5:0.3.

[0017] Further, the step four further comprises the following steps:

[0018] 0.5-2 parts of the second-stage composite activator is added, and stirring is conducted for 3 hours.

[0019] Further, the second-stage composite activator is n-eicosane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and N-hydroxysuccinimide mixed uniformly at a parts ratio of 100:30:10.

[0020] Further, the composite antioxidant in the step five is any one or a combination of multiple of the following:

[0021] 2,6-di-tert-butyl-4-methylphenol, tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecanol, tris(2,4-di-tert-butylphenyl)phosphite, sodium borohydride, N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, sodium sulfite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, dioctadecyl pentaerythritol diphosphite.

[0022] Further, the composite catalyst in the step four is 4-dimethylaminopyridine, phosphorous acid, boric acid and stannous chloride mixed uniformly at a molar ratio of 1:0.5:0.3:0.1.

[0023] Further, the step five further comprises the following steps:

[0024] Cool down to 120 ℃, inject liquid CO2 to carry out supercritical extraction, separate unreacted ethylenediamine and oligomers, and then cut and form underwater through a double-screw extruder.

[0025] The general anti-yellowing ethylene bis-stearamide prepared by the above synthesis process is also within the protection scope of the present application.

[0026] The present application has the following beneficial effects:

[0027] The present application uses stearic acid as the main raw material, adds ethylenediamine to carry out organic synthesis reaction, deeply studies the whole reaction process, uses different catalysts and activators according to different reaction stages and reaction mechanisms, finally adds suitable composite antioxidant, and then prepares the general anti-yellowing ethylene bis-stearamide, which can effectively solve the yellowing problem of products added with ethylene bis-stearamide. DETAILED DESCRIPTION

[0028] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the protection scope of the present application.

[0029] Embodiment 1

[0030] A synthesis process of a general anti-yellowing ethylene bis-stearamide includes the following steps:

[0031] The reaction system is replaced with nitrogen, and the nitrogen concentration is detected to be more than 99.9%;

[0032] Put 1000 parts of stearic acid into the reaction kettle, start heating, and when the stearic acid is completely melted and the temperature reaches 85°C, add 0.3 parts of the first-stage composite activator (phosphoric acid, sodium dihydrogen phosphate, and p-toluenesulfonic acid are uniformly mixed in a molar ratio of 1:0.3:0.3), stir for 10 min, and then add 110 parts of ethylenediamine to the reaction system at a drop rate of 5.5 parts per minute. After the drop is completed, stir for 1 hour to form stable molecular pairing under the action of the first-stage composite activator. Increase the temperature to 175°C at a rate of 0.5°C / hr, and when the temperature reaches 135°C, add 2 parts of the composite catalyst (4-dimethylaminopyridine, phosphorous acid, and boric acid are uniformly mixed in a molar ratio of 1:0.5:0.3). Collect the condensed water produced by the condensation reaction through a condensing device. When the water output is less than 0.3 g / 10 min, reduce the temperature to 165°C, add 0.5 parts of the second-stage composite activator (n-eicosane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, and N-hydroxysuccinimide are uniformly mixed in a parts ratio of 100:30:10), and stir for 3 hours to convert the by-products. Add 0.5 parts of the composite antioxidant to the material, continue stirring for 30 min to ensure uniform dissolution and dispersion, rapidly cool and shape, and a high-temperature-resistant and yellowing-resistant ethylene bis-stearamide is obtained.

[0033] Example 2

[0034] In Example 1, the amount of the first-stage composite activator is adjusted to 0.6 parts, and the other steps are the same as in Example 1.

[0035] Example 3

[0036] In Example 1, the amount of the first-stage composite activator is adjusted to 1 part, and the other steps are the same as in Example 1.

[0037] The results are shown in Table 1.

[0038] Table 1

[0039] Example Acid value Amine value Colour number 250°C colour number 1 7.48 2.44 3 5 2 5.89 1.65 3 4 3 5.90 1.78 3 4

[0040] Example 4

[0041] In Example 1, the amount of the composite catalyst is adjusted to 3 parts.

[0042] Example 5

[0043] In Example 1, the amount of the composite catalyst is adjusted to 4 parts.

[0044] Example 6

[0045] In Example 1, the amount of the composite catalyst is adjusted to 5 parts. The results are shown in Table 2.

[0046] Table 2

[0047] Example Acid value Amine value Colour number 250°C colour number 1 7.48 2.44 3 5 4 6.67 2.05 3 5 5 6.02 1.78 3 5 6 5.98 1.66 3 5

[0048] Example 7

[0049] The amount of the second-stage composite activator in the second paragraph of Example 1 is adjusted to 1 part; Example 8

[0050] The amount of the second-stage composite activator in the second paragraph of Example 1 is adjusted to 2 parts; Example 9

[0051] The amount of the second-stage composite activator in the second paragraph of Example 1 is adjusted to 3 parts; the results are shown in Table 3:

[0052] Table 3

[0053] Example Acid value Amine value Colour number 250°C colour number 1 7.48 2.44 3 5 7 6.88 1.95 3 4 8 6.65 1.90 3 3 9 6.70 2.00 3 3

[0054] Example 10

[0055] This embodiment is an improvement based on Examples 1-9, a general anti-yellowing ethylene bis-stearamide synthesis process, including the following steps:

[0056] Put 1000 parts of stearic acid into a reaction kettle, start heating, and when the stearic acid is completely melted and the temperature reaches 85°C, add 0.6 parts of the first-stage composite activator (phosphoric acid, sodium dihydrogen phosphate and p-toluenesulfonic acid are mixed uniformly at a molar ratio of 1:0.3:0.3), stir for 10 min, add 110 parts of ethylenediamine to the reaction system at a drop rate of 5.5 parts per minute, stir for 1 hour after the drop is completed, and heat to 175°C at a heating rate of 0.5°C / hr. When the temperature reaches 135°C, add 4 parts of the composite catalyst (4-dimethylaminopyridine, phosphorous acid and boric acid are mixed uniformly at a molar ratio of 1:0.5:0.3), continuously collect the condensate water, when the output water amount is less than 0.3 g / 10 min, reduce the temperature to 165°C, add 1 part of the second-stage composite activator (n-eicosane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, N-hydroxysuccinimide are mixed uniformly at a parts ratio of 100:30:10), stir for 3 hours, add 0.5 parts of the composite antioxidant to the material, continuously stir for 30 min, and rapidly cool and shape;

[0057] The results are shown in Table 4:

[0058] Table 4

[0059] Example Acid value Amine value Colour number 250°C colour number 1 7.48 2.44 3 5 10 4.80 0.82 2 2

[0060] Example 11

[0061] This embodiment is an improvement based on Example 10, which cancels the first-stage composite activator, a general anti-yellowing ethylene bis-stearamide synthesis process, including the following steps:

[0062] Put 1000 parts of stearic acid into the reaction kettle, start heating, when the stearic acid is completely melted and the temperature reaches 85°C, add 0.6 parts of the first-stage composite activator (phosphoric acid, sodium dihydrogen phosphate and p-toluenesulfonic acid are uniformly mixed in a molar ratio of 1:0.3:0.3), stir for 10 min, add 110 parts of ethylenediamine to the reaction system at a dropwise adding speed of 5.5 parts per minute, stir for 1 hour after the dropwise adding is completed, and heat to 175°C at a heating speed of 0.5°C / hr; when the temperature reaches 135°C, add 4 parts of the composite catalyst (4-dimethylaminopyridine, phosphorous acid and boric acid are uniformly mixed in a molar ratio of 1:0.5:0.3), continuously collect the condensed water, when the water output is less than 0.3 g / 10 min, reduce the temperature to 165°C, add 0.5 parts of the composite antioxidant to the material, continuously stir for 30 min, and rapidly cool and shape;

[0063] Example 12

[0064] This example is an improvement based on Example 10, and the second-stage composite activator is cancelled. A general type of anti-yellowing ethylene bis-stearamide synthesis process includes the following steps:

[0065] Put 1000 parts of stearic acid into the reaction kettle, start heating, when the stearic acid is completely melted and the temperature reaches 85°C, add 0.6 parts of the first-stage composite activator (phosphoric acid, sodium dihydrogen phosphate and p-toluenesulfonic acid are uniformly mixed in a molar ratio of 1:0.3:0.3), stir for 10 min, add 110 parts of ethylenediamine to the reaction system at a dropwise adding speed of 5.5 parts per minute, stir for 1 hour after the dropwise adding is completed, and heat to 175°C at a heating speed of 0.5°C / hr; when the temperature reaches 135°C, add 4 parts of the composite catalyst (4-dimethylaminopyridine, phosphorous acid and boric acid are uniformly mixed in a molar ratio of 1:0.5:0.3), continuously collect the condensed water, when the water output is less than 0.3 g / 10 min, reduce the temperature to 165°C, add 0.5 parts of the composite antioxidant to the material, continuously stir for 30 min, and rapidly cool and shape;

[0066] The results are shown in Table 5:

[0067] Table 5

[0068] Example Acid value Amine value Colour number 250°C colour number Example Acid value Amine value Colour number 250°C colour number 10 4.80 0.82 2 2 11 9.47 1.86 4 6 12 5.94 1.40 3 4

[0069] To sum up, the application has good stability and catalysis for the whole reaction process, and the heat resistance of the finished product is stable. The universal anti-yellowing ethylene bis-stearamide can significantly improve the processing efficiency and stability. Compared with the current production process, the application can effectively improve the purity of the product, reduce discoloration, and improve thermal stability.

[0070] Example 13

[0071] This embodiment is an improvement on the basis of example 1, a universal anti-yellowing ethylene bis-stearamide synthesis process, including the following steps:

[0072] The reaction system is replaced with nitrogen, and the nitrogen concentration is detected to be more than 99.9%;

[0073] Put 1000 parts of stearic acid into the reaction kettle, start heating, and when the stearic acid is completely melted and the temperature reaches 85℃, add 0.3 parts of the first-stage composite activator (phosphoric acid, sodium dihydrogen phosphate and p-toluenesulfonic acid are mixed uniformly in a molar ratio of 1:0.3:0.3), stir for 10 min, add 110 parts of ethylenediamine to the reaction system at a drop rate of 5.5 parts per minute, stir for 1 hour after the drop is completed, so that it forms a stable molecular pair under the action of the first-stage composite activator; heat to 175℃ at a heating rate of 0.5℃ / hr, when the temperature reaches 135℃, add 2 parts of composite catalyst (4-dimethylaminopyridine, phosphorous acid, boric acid and stannous chloride are mixed uniformly in a molar ratio of 1:0.5:0.3:0.1), and then form a four-component catalytic system, which greatly shortens the reaction time and improves the conversion rate; continuously collect the condensate water, when the water output is less than 0.3g / 10min, reduce the temperature to 165℃, add 0.5 parts of the second-stage composite activator (n-eicosane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, N-hydroxysuccinimide are mixed uniformly in a parts ratio of 100:30:10), stir for 3 hours, then add 0.5 parts of composite antioxidant to the material, continue to stir for 30 min, and finally rapidly cool and shape.

[0074] Example 14

[0075] This embodiment is an improvement on the basis of example 1, a universal anti-yellowing ethylene bis-stearamide synthesis process, including the following steps:

[0076] First, the reaction system is replaced with nitrogen, and the nitrogen concentration is detected to be more than 99.9%;

[0077] Put 1000 parts of stearic acid into the reaction kettle, start heating, and when the stearic acid is completely melted and the temperature reaches 85°C, add 0.3 parts of the first composite activator (phosphoric acid, sodium dihydrogen phosphate and p-toluenesulfonic acid are mixed uniformly in a molar ratio of 1:0.3:0.3), stir for 10 min, add 110 parts of ethylenediamine to the reaction system at a dropwise addition rate of 5.5 parts per minute, and after the dropwise addition is completed, stir for 1 hour to form stable molecular pairing under the action of the first composite activator; increase the temperature to 175°C at a rate of 0.5°C / hr, and when the temperature reaches 135°C, add 2 parts of the composite catalyst (4-dimethylaminopyridine, phosphorous acid and boric acid are mixed uniformly in a molar ratio of 1:0.5:0.3), continuously collect the condensed water, when the water output is less than 0.3g / 10min, reduce the temperature to 165°C, add 0.5 parts of the second composite activator (n-eicosane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, N-hydroxysuccinimide are mixed uniformly in a parts ratio of 100:30:10), stir for 3 hours, then add 0.5 parts of the composite antioxidant to the material, continuously stir for 30 min, then reduce the temperature to 120°C and inject liquid CO2 for supercritical extraction, separate the unreacted ethylenediamine and oligomers, then cut and form into particles underwater through a double-screw extruder, thereby increasing the raw material recovery rate by more than 25%, the product particle size distribution is uniform, and the melting index stability is further improved.

[0078] Further, a new synthesis process is used to prepare a general-purpose anti-yellowing ethylene bis-stearamide to effectively treat the color change problem of the processed product.

[0079] The embodiments described in the specification are only representative embodiments in the process of the present application, and any modifications or adjustments made by those skilled in the art based on the content of the present application are within the scope of the present application.

[0080] In the description of the specification, the description of the terms "one embodiment", "example", "specific example" and the like means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In the specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

Claims

1. A synthesis process for a general-purpose anti-yellowing ethylene bis-stearamide, characterized in that, Includes the following steps: Step 1: Replace the reaction system with nitrogen gas and check that the nitrogen concentration reaches 99.9% or higher; Step 2: Place 1000 parts of stearic acid into the reaction vessel and begin heating; Step 3: After the stearic acid has completely melted, heat the mixture to 80-95°C and add 110-150 parts of ethylenediamine to the reaction system at a dropping rate of 5.5 parts per minute. Stir for 1 hour after the addition is complete. Step 4: Increase the temperature to 175-180℃ at a rate of 0.5℃ / hr. When the temperature reaches 135℃, add 2-5 parts of composite catalyst and continue to collect the condensate. When the output water is less than 0.3g / 10min, reduce the temperature to 160-165℃. Step 5: Add 0.5-2 parts of compound antioxidant to the material, stir continuously for 30 minutes, and then quickly cool and mold. Step two also includes the following steps: Once the stearic acid has completely melted and the temperature reaches 85°C, add 0.3-1 part of the first-stage composite activator and stir for 10 minutes. The first composite activator is prepared by uniformly mixing phosphoric acid, sodium dihydrogen phosphate and p-toluenesulfonic acid in a molar ratio of 1:0.3:0.3; The composite catalyst in step four is prepared by uniformly mixing 4-dimethylaminopyridine, phosphorous acid and boric acid in a molar ratio of 1:0.5:0.3 or 4-dimethylaminopyridine, phosphorous acid, boric acid and stannous chloride in a molar ratio of 1:0.5:0.3:0.

1. Step four also includes the following steps: Add 0.5-2 parts of the second-stage composite activator and stir for 3 hours; The second composite activator is prepared by uniformly mixing n-eicosane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, and N-hydroxysuccinimide in a ratio of 100:30:

10.

2. The synthesis process of a general-purpose anti-yellowing ethylene bis-stearamide according to claim 1, characterized in that, The composite antioxidant in step five is any one or more of the following combinations: 2,6-Di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris(2,4-di-tert-butylphenyl)phosphite, sodium borohydride, N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine, sodium sulfite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bisoctadecyl pentaerythritol diphosphite.

3. The synthesis process of a general-purpose anti-yellowing ethylene bis-stearamide according to claim 1, characterized in that, Step five also includes the following steps: When the temperature is lowered to 120°C, liquid CO2 is injected for supercritical extraction to separate unreacted ethylenediamine and oligomers. The mixture is then pelletized underwater using a twin-screw extruder.

4. A general-purpose anti-yellowing ethylene bis-stearamide, characterized in that, The general-purpose anti-yellowing ethylene bis-stearamide is prepared by the synthesis process described in any one of claims 1-3.