Synthetic process of universal anti-yellowing ethylene bisstearamide

Abstract

The invention discloses a synthesis process of universal anti-yellowing ethylene bisstearamide, and relates to the technical field of organic chemical synthesis. The method comprises the following steps: 1, replacing a reaction system with nitrogen, and detecting that the concentration of the nitrogen reaches 99.9% or above; 2, 1000 parts of stearic acid is put into a reaction kettle, and heating is started; 3, after the stearic acid is completely melted, the temperature is increased to 80-95 DEG C, 110-150 parts of ethidene diamine is added into the reaction system at the dropwise adding speed of 5.5 parts per minute, and stirring is conducted for 1 hour after dropwise adding is completed; according to the preparation method, stearic acid is taken as a main raw material, ethidene diamine is added for organic synthesis reaction, different catalysts and activators are adopted according to different reaction sections and reaction mechanisms, and a proper complex antioxidant is added, so that universal anti-yellowing ethylene bisstearamide is prepared; the problem of yellowing of a product added with ethylene bis stearamide can be effectively solved.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic chemical synthesis, and particularly relates to a synthesis process of a general-purpose anti-yellowing ethylene bisstearamide. Background Art

[0003] Ethylene bisstearamide contains two amide groups -CO-NH- in its molecular structure. Therefore, in the synthesis reaction, various by-products are easily generated, making the material extremely prone to coloring during the reaction process, the finished product having low purity and poor heat resistance, and there is a problem of color change in the processed product, which limits its application in products.

[0004] Based on this, a synthesis process of a general-purpose anti-yellowing ethylene bisstearamide is proposed to meet the requirements of high-end plastic products. Summary of the Invention

[0005] The purpose of the present invention is to provide a synthesis process of a general-purpose anti-yellowing ethylene bisstearamide to solve the existing problems: Ethylene bisstearamide contains two amide groups -CO-NH- in its molecular structure. Therefore, in the synthesis reaction, various by-products are easily generated, making the material extremely prone to coloring during the reaction process, the finished product having low purity and poor heat resistance, and there is a problem of color change in the processed product, which limits its application in products.

[0006] To solve the above technical problems, the present invention is achieved through the following technical solutions:

[0007] The present invention is a synthesis process of a general-purpose anti-yellowing ethylene bisstearamide, including the following steps:

[0008] Step 1: Replace the reaction system with nitrogen and detect that the nitrogen concentration reaches more than 99.9%;

[0009] Step 2: Put 1000 parts of stearic acid into the reaction kettle and start heating;

[0010] Step 3: Wait until the stearic acid is completely melted and heated 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. After the dropping is completed, stir for 1 hour;

[0011] Step 4: Heat to 175 - 180°C at a heating rate of 0.5°C / hr. When the temperature reaches 135°C, add 2 - 5 parts of a composite catalyst, continuously collect the condensed water. When the water production is less than 0.3 g / 10 min, lower the temperature to 160 - 165°C;

[0012] Step 5: Add 0.5 - 2 parts of a composite antioxidant to the material, continuously stir for 30 min, and quickly cool and form.

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

[0014] When the stearic acid is completely melted and the temperature reaches 85 °C, add 0.3 - 1 part of the first-stage composite activator and stir for 10 min.

[0015] Further, the first-stage 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.

[0016] Further, 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.

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

[0018] Add 0.5 - 2 parts of the second-stage composite activator and stir for 3 hours.

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

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

[0021] 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, mercaptomethyltin, N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, sodium sulfite, sodium bisulfate, bis(2,6-diisopropylphenyl)carbodiimide, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite.

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

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

[0024] Cool down to 120 °C and inject liquid CO2 for supercritical extraction to separate unreacted ethylenediamine and oligomers, and then pelletize underwater through a twin-screw extruder.

[0025] The general-purpose anti-yellowing ethylene bisstearamide prepared by the above synthesis process is also within the protection scope of the present invention.

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

[0027] In the present invention, stearic acid is used as the main raw material and ethylenediamine is added for an organic synthesis reaction. The whole reaction process is deeply studied. For different reaction segments and reaction mechanisms, different catalysts and activators are used. Finally, a suitable compound antioxidant is added, and then a general-purpose anti-yellowing ethylene bisstearamide is prepared, which can effectively solve the problem of yellowing of products added with ethylene bisstearamide. Specific embodiments

[0028] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention.

[0029] Example 1

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

[0031] The reaction system is purged with nitrogen, and the nitrogen concentration is detected to be above 99.9%;

[0032] 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 0.3 part of the first-stage compound activator (phosphoric acid, sodium dihydrogen phosphate and p-toluenesulfonic acid are mixed evenly at a molar ratio of 1:0.3:0.3), stir for 10 minutes, and add 110 parts of ethylenediamine to the reaction system at a dropping rate of 5.5 parts per minute. After the dropping is completed, stir for 1 hour to form a stable molecular pairing under the action of the first-stage compound activator; heat up to 175°C at a heating rate of 0.5°C / hr. When the temperature reaches 135°C, add 2 parts of the compound catalyst (4-dimethylaminopyridine, phosphorous acid and boric acid are mixed evenly at a molar ratio of 1:0.5:0.3). Continuously collect the condensed water generated by the condensation reaction through the condensation device. When the water production is less than 0.3 g / 10 min, lower the temperature to 165°C, add 0.5 part of the second-stage compound activator (n-eicosane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, N-hydroxysuccinimide are mixed evenly at a ratio of 100:30:10 by parts), stir for 3 hours, and then convert the by-products. Add 0.5 part of the compound antioxidant to the material, continuously stir for 30 minutes to ensure uniform dissolution and dispersion, and quickly cool and form to obtain a high-temperature resistant and anti-yellowing ethylene bisstearamide;

[0033] Example 2

[0034] Adjust the addition amount of the first-stage composite activator in Example 1 to 0.6 parts, and keep other steps the same as in Example 1;

[0035] Example 3

[0036] Adjust the addition amount of the first-stage composite activator in Example 1 to 1 part, and keep other steps the same as in Example 1;

[0037] The results are compared as shown in Table 1:

[0038] Table 1

[0039] Example Acid value Amine value Color number Color number at 250 °C 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] Adjust the addition amount of the composite catalyst in Example 1 to 3 parts;

[0042] Example 5

[0043] Adjust the addition amount of the composite catalyst in Example 1 to 4 parts;

[0044] Example 6

[0045] Adjust the addition amount of the composite catalyst in Example 1 to 5 parts;

[0046] The results are compared as shown in Table 2:

[0047] Table 2

[0048]

[0049]

[0050] Example 7

[0051] Adjust the addition amount of the second-stage composite activator in Example 1 to 1 part;

[0052] Example 8

[0053] Adjust the addition amount of the second-stage composite activator in Example 1 to 2 parts;

[0054] Example 9

[0055] Adjust the addition amount of the second-stage composite activator in Example 1 to 3 parts;

[0056] The results are compared as shown in Table 3:

[0057] Table 3

[0058] Example Acid value Amine value Color number Color number at 250 °C 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

[0059] Example 10

[0060] This example is an improvement based on Examples 1-9. A synthesis process of a general-purpose anti-yellowing ethylene bisstearamide includes the following steps:

[0061] Put 1000 parts of stearic acid into a reaction kettle, start heating up. After the stearic acid is completely melted and the temperature reaches 85 °C, add 0.6 part of the first-stage composite activator (phosphoric acid, sodium dihydrogen phosphate and p-toluenesulfonic acid are mixed evenly 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 dropping rate of 5.5 parts per minute. After the dropping is completed, stir for 1 hour, heat up 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 evenly in a molar ratio of 1:0.5:0.3), continuously collect the condensed water. When the water production is less than 0.3 g / 10 min, lower 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 evenly in a parts ratio of 100:30:10), stir for 3 hours, then add 0.5 part of the composite antioxidant to the material, continuously stir for 30 min, and quickly cool and form;

[0062] The results of the comparison are shown in Table 4:

[0063] Table 4

[0064] Example Acid value Amine value Color number Color number at 250 °C 1 7.48 2.44 3 5 10 4.80 0.82 2 2

[0065] Example 11

[0066] This example is an improvement based on Example 10. The first-stage composite activator is cancelled. A synthesis process of a general-purpose anti-yellowing ethylene bisstearamide includes the following steps:

[0067] Put 1000 parts of stearic acid into a reaction kettle, start heating up. After the stearic acid is completely melted and the temperature reaches 85 °C, add 110 parts of ethylenediamine to the reaction system at a dropping rate of 5.5 parts per minute. After the dropping is completed, stir for 1 hour, heat up 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 evenly in a molar ratio of 1:0.5:0.3), continuously collect the condensed water. When the water production is less than 0.3 g / 10 min, lower 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 evenly in a parts ratio of 100:30:10), stir for 3 hours, then add 0.5 part of the composite antioxidant to the material, continuously stir for 30 min, and quickly cool and form;

[0068] Example 12

[0069] This example is an improvement based on Example 10. It is a synthesis process of a general-purpose anti-yellowing ethylene bisstearamide, which cancels the second-stage composite activator and includes the following steps:

[0070] Put 1000 parts of stearic acid into the reaction kettle and start heating. When the stearic acid is completely melted and the temperature reaches 85°C, add 0.6 part of the first-stage composite activator (phosphoric acid, sodium dihydrogen phosphate, and p-toluenesulfonic acid are mixed evenly in a molar ratio of 1:0.3:0.3), stir for 10 minutes, and add 110 parts of ethylenediamine to the reaction system at a dropping rate of 5.5 parts per minute. After the dropping is completed, stir for 1 hour, and heat up 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 evenly in a molar ratio of 1:0.5:0.3), continuously collect the condensed water. When the water production is less than 0.3 g / 10 min, lower the temperature to 165°C, add 0.5 part of the composite antioxidant to the material, and continuously stir for 30 minutes, then quickly cool and form;

[0071] The results are compared as shown in Table 5:

[0072] Table 5

[0073] Example Acid value Amine value Color number Color number at 250 °C 10 4.80 0.82 2 2 11 9.47 1.86 4 6 12 5.94 1.40 3 4

[0074] In summary, the complete analysis of the entire reaction process and the reaction mechanism formulated in stages of the present invention have good stability and catalytic effects. The heat resistance of the finished product is stable. Adding the general-purpose anti-yellowing ethylene bisstearamide of the present invention can significantly improve the processing efficiency and stability. Compared with the currently commonly used production processes, experiments show that the present invention can effectively improve the purity of the product, reduce color change, and improve thermal stability.

[0075] Example 13

[0076] This example is an improvement based on Example 1. It is a synthesis process of a general-purpose anti-yellowing ethylene bisstearamide, which includes the following steps:

[0077] Replace the reaction system with nitrogen and detect that the nitrogen concentration reaches more than 99.9%;

[0078] Put 1000 parts of stearic acid into the reaction kettle and start heating up. Wait until the stearic acid is completely melted and the temperature reaches 85°C, then add 0.3 part of the first-stage composite activator (phosphoric acid, sodium dihydrogen phosphate and p-toluenesulfonic acid are mixed evenly at a molar ratio of 1:0.3:0.3), stir for 10 min, and add 110 parts of ethylenediamine to the reaction system at a dropping rate of 5.5 parts per minute. After the dropping is completed, stir for 1 hour to form stable molecular pairing under the action of the first-stage composite activator; heat up to 175°C at a heating rate of 0.5°C / hr. When the temperature reaches 135°C, add 2 parts of the composite catalyst (4-dimethylaminopyridine, phosphorous acid, boric acid and stannous chloride are mixed evenly at a molar ratio of 1:0.5:0.3:0.1) to form a quaternary catalytic system, which greatly shortens the reaction time and improves the conversion rate; continuously collect the condensed water. When the water production is less than 0.3 g / 10 min, lower the temperature to 165°C, add 0.5 part of the second-stage composite activator (n-eicosane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, N-hydroxysuccinimide are mixed evenly at a ratio of 100:30:10 by parts), stir for 3 hours, then add 0.5 part of the composite antioxidant to the material, continuously stir for 30 min, and finally quickly cool down and form.

[0079] Example 14

[0080] This example is an improvement based on Example 1. A synthesis process of a general-purpose anti-yellowing ethylene bisstearamide includes the following steps:

[0081] First, displace the reaction system with nitrogen and detect that the nitrogen concentration reaches more than 99.9%;

[0082] Put 1000 parts of stearic acid into the reaction kettle and start heating up. When the stearic acid is completely melted and the temperature reaches 85°C, add 0.3 part of the first-stage composite activator (phosphoric acid, sodium dihydrogen phosphate, and p-toluenesulfonic acid are mixed evenly at a molar ratio of 1:0.3:0.3), stir for 10 min, and add 110 parts of ethylenediamine to the reaction system at a dropping rate of 5.5 parts per minute. After the dropping is completed, stir for 1 hour to form a stable molecular pairing under the action of the first-stage composite activator; heat up to 175°C at a heating rate of 0.5°C / hr. When the temperature reaches 135°C, add 2 parts of the composite catalyst (4-dimethylaminopyridine, phosphorous acid, and boric acid are mixed evenly at a molar ratio of 1:0.5:0.3), continuously collect the condensed water. When the water production is less than 0.3 g / 10 min, lower the temperature to 165°C, add 0.5 part of the second-stage composite activator (n-eicosane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, and N-hydroxysuccinimide are mixed evenly at a ratio of 100:30:10 by parts), stir for 3 hours, then add 0.5 part of the composite antioxidant to the material, continuously stir for 30 min, and then lower the temperature to 120°C and inject liquid CO2 for supercritical extraction to separate the unreacted ethylenediamine and oligomers. Subsequently, underwater pelletize through a twin-screw extruder to further increase the raw material recovery rate by more than 25%, with the product particle size distribution being uniform and the melt index stability being further improved.

[0083] Furthermore, a new synthesis process is used to prepare a general-purpose anti-yellowing ethylene bisstearamide to effectively address the problem of color change in the processed product.

[0084] The embodiments described in this specification are only representative embodiments in the process of the present invention. Modifications or adjustments made by those skilled in the relevant technical fields according to the content of this invention patent all fall within the protection scope of the present invention.

[0085] In the description of this specification, the description with reference to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

Claims

1. A synthesis process of a general anti-yellowing ethylene bisstearic acid amide, characterized in that: The following steps are involved: Step 1: Replace the reaction system with nitrogen and detect that the nitrogen concentration is above 99.9%; Step 2: Place 1000 parts of stearic acid into a reaction kettle and start heating; Step 3: After the stearic acid is completely melted and heated to 80-95°C, 110-150 parts of ethylenediamine are added to the reaction system at a drop rate of 5.5 parts per minute, and stirred for 1 hour after the drop addition is completed; Step 4: Raise the temperature to 175-180°C at a rate of 0.5°C / hr. When the temperature reaches 135°C, add 2-5 parts of the composite catalyst and continue to collect condensed water. When the output water volume is less than 0.3g / 10min, lower the temperature to 160-165°C. Step 5: Add 0.5-2 parts of compound antioxidant to the material, continue stirring for 30 minutes, and quickly cool down to form.

2. The synthesis process of a general anti-yellowing ethylene bisstearic acid amide according to claim 1, characterized in that: The step 2 also includes the following steps: When the stearic acid is completely melted and the temperature reaches 85°C, add 0.3-1 part of the first stage composite activator and stir for 10 minutes.

3. The synthesis process of a general anti-yellowing ethylene bisstearic acid amide according to claim 2, characterized in that: The first-stage 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.

4. The synthesis process of a general anti-yellowing ethylene bisstearic acid amide according to claim 1, characterized in that: The composite catalyst in step 4 is prepared by uniformly mixing 4-dimethylaminopyridine, phosphorous acid and boric acid in a molar ratio of 1:0.5:0.

3.

5. The synthesis process of a general anti-yellowing ethylene bisstearic acid amide according to claim 1, characterized in that: The step 4 also includes the following steps: Add 0.5-2 parts of the second stage composite activator and stir for 3 hours.

6. The synthesis process of a general-purpose anti-yellowing ethylene bisstearic acid amide according to claim 5, characterized in that: The second-stage composite activator is prepared by uniformly mixing n-eicosane, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and N-hydroxysuccinimide in a ratio of 100:30:

10.

7. The synthesis process of a general-purpose anti-yellowing ethylene bisstearic acid amide according to claim 1, characterized in that: The composite antioxidant in step 5 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, methyltin mercaptan, N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, sodium sulfite, sodium bisulfate, bis(2,6-diisopropylphenyl)carbodiimide, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, dioctadecylpentaerythritol diphosphite.

8. The synthesis process of a general-purpose anti-yellowing ethylene bisstearic acid amide according to claim 1, characterized in that: The composite catalyst in step 4 is prepared by uniformly mixing 4-dimethylaminopyridine, phosphorous acid, boric acid and stannous chloride in a molar ratio of 1:0.5:0.3:0.

1.

9. The synthesis process of a general-purpose anti-yellowing ethylene bisstearic acid amide according to claim 1, characterized in that: The step five also includes the following steps: When the temperature drops to 120°C, liquid CO2 is injected for supercritical extraction to separate unreacted ethylenediamine and oligomers, followed by underwater pelletization through a twin-screw extruder.

10. A general-purpose anti-yellowing ethylene bisstearic acid amide, characterized in that: The universal anti-yellowing ethylene bisstearic acid amide is prepared by the synthesis process described in any one of claims 1 to 9.

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