CN113402413B - Lubricant Ethylene Bis Stearamide (EBS) and preparation method thereof - Google Patents
Lubricant Ethylene Bis Stearamide (EBS) and preparation method thereof Download PDFInfo
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- CN113402413B CN113402413B CN202110574411.1A CN202110574411A CN113402413B CN 113402413 B CN113402413 B CN 113402413B CN 202110574411 A CN202110574411 A CN 202110574411A CN 113402413 B CN113402413 B CN 113402413B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/36—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
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Abstract
The application relates to the technical field of lubricant synthesis, in particular to a lubricant Ethylene Bis Stearamide (EBS) and a preparation method thereof. The lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 100 parts of stearic acid, 0.5-1.0 part of compound catalyst, 0.20-0.45 part of antioxidant and 11.7-12.8 parts of ethylenediamine; the antioxidant is one or more of 2, 6-di-tert-butyl-p-cresol, 2- (2-hydroxy-3, 5-ditert-amyl-phenyl) benzotriazole, poly (4-hydroxy-2, 6-tetramethyl-1-piperidineethanol) succinate, 4' methylenebis (2, 6-di-tert-butylphenol), beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) propionic acid n-octadecyl ester and tris (2, 4-tert-butylphenyl) phosphite. The ethylene bis stearamide prepared in the application is not easy to yellow, is white and clean compared with a commercially available finished product, and has the advantages of good color and luster and high quality of the finished product.
Description
Technical Field
The application relates to the technical field of lubricant synthesis, in particular to a lubricant Ethylene Bis Stearamide (EBS) and a preparation method thereof.
Background
The vinyl bis stearamide, also known as N, N' -ethylene bis stearamide, contains polar amide groups and two hydrophobic groups with long carbon chains, has the characteristics of high-temperature lubricity, low-temperature anti-sticking property and the like, and is widely used for plastic lubricants, casting lubricants, metal processing lubricants, bone lubricating agents for powder metallurgy, anti-sticking agents, viscosity regulators, anti-corrosion agents, surface brightening agents and the like.
Currently, vinyl bis stearamide is produced by esterification of stearic acid, ethylene diamine, and a catalyst. The method is characterized in that N-acylation reaction is carried out, electrophilic substitution reaction is carried out on amino nitrogen atoms, partial positive charges are carried on carbon atoms of carboxyl in acylating agent stearic acid, the carbon atoms can interact with lone pair electrons on the amino nitrogen atoms to form a transition state complex, and ammonium salt is converted into amide after high-temperature dehydration. The existing preparation method of vinyl bis stearamide comprises the steps of heating stearic acid and a phosphoric acid catalyst to be hot melted under normal pressure, heating the temperature to 80-100 ℃ for synthesis, dropwise adding ethylenediamine, wherein the molar ratio of ethylenediamine to stearic acid is 2.05: 1, keeping the temperature for 20 minutes after all ethylenediamine is added, and carrying out dehydration reaction on ammonium salt at 170-180 ℃ for 2-3 hours.
In view of the preparation method of the vinyl bis-stearamide in the related art, the applicant finds that the related art has the following defects: the prepared final product has yellow color, higher color and lower product quality.
Disclosure of Invention
In order to solve the problems of yellow color, high color and luster and low product quality of the ethylene bis-stearamide, the application aims to provide the lubricant ethylene bis-stearamide (EBS) and the preparation method thereof.
In a first aspect, the present application provides a lubricant Ethylene Bis Stearamide (EBS), which is prepared from the following raw materials in parts by weight: 100 parts of stearic acid, 0.5-1.0 part of compound catalyst, 0.20-0.45 part of antioxidant and 11.7-12.8 parts of ethylenediamine; the antioxidant is one or a combination of more of 2, 6-di-tert-butyl-p-cresol, 2- (2-hydroxy-3, 5-ditert-amyl-phenyl) benzotriazole, poly (4-hydroxy-2, 6-tetramethyl-1-piperidineethanol) succinate, 4' methylenebis (2, 6-di-tert-butylphenol), n-octadecyl beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) propionate and tri (2, 4-tert-butylphenyl) phosphite.
By adopting the technical scheme, the specific antioxidant is adopted in the application, so that the finally obtained ethylene bis-stearamide is not easy to yellow, and is white and clean compared with a commercially available finished product, the color is better, the obtained ethylene bis-stearamide has a lower amine value, good thermal stability and higher quality of the finished product.
Preferably, the compound catalyst consists of phosphoric acid and phosphorous acid; the mass of the phosphoric acid accounts for 28.0-36.0% of the total mass of the compound catalyst, and the mass of the phosphorous acid accounts for 64.0-72.0% of the total mass of the compound catalyst.
By adopting the technical scheme, the improvement of the integral esterification rate is facilitated, the material consumption is reduced, the resource utilization rate is improved, and the energy consumption of the purification operation can be reduced.
Preferably, the stearic acid has a color of 30APHA or less and does not change color in a molten state.
By adopting the technical scheme, the chromaticity of the final product can be ensured, and the finally obtained ethylene bis stearamide is not easy to yellow.
Preferably, the content of the ethylenediamine is more than 99.8%, the color is less than 10APHA, and the turbid and discoloring phenomena are avoided.
By adopting the technical scheme, the color of the final product can be ensured, and the finally obtained ethylene bis stearamide is not easy to yellow.
Preferably, the antioxidant consists of 2, 6-di-tert-butyl-p-cresol and poly (4-hydroxy-2, 6-tetramethyl-1-piperidineethanol) succinate; the 2, 6-di-tert-butyl-p-cresol accounts for 75-90% of the total mass of the antioxidant.
By adopting the technical scheme, the yellowing probability of the final product can be reduced, and the whiteness and the color of the final product are ensured.
Preferably, the antioxidant consists of n-octadecyl beta- (4-hydroxyphenyl 3, 5-di-tert-butyl) propionate and tri (2, 4-tert-butylphenyl) phosphite; the beta- (4-hydroxyphenyl 3, 5-di-tert-butyl) n-octadecyl propionate accounts for 88-96% of the total weight of the antioxidant.
By adopting the technical scheme, the yellowing probability of the final product can be reduced, and the whiteness and the color of the final product are ensured.
In a second aspect, the present application provides a method for preparing a lubricant Ethylene Bis Stearamide (EBS), comprising the steps of:
step one, weighing stearic acid, a compound catalyst and an antioxidant according to a ratio, and adding the stearic acid, the compound catalyst and the antioxidant which are accurately weighed into an esterification reactor;
step two, after protective gas is introduced into the esterification reactor, heating at the speed of 0.5-1.0 ℃/min until stearic acid is completely melted, and starting stirring;
step three, heating to 100 ℃, and dropwise adding ethylenediamine, wherein the dropwise adding time is controlled to be 40-60min;
step four, after the dropwise adding is finished, heating to 130 ℃, preserving heat for 1 hour, then heating to 200 ℃, preserving heat for 4-6 hours, and dehydrating;
and step five, sampling and analyzing, stopping the reaction when the acid value is less than 10mgKOH/g, cooling to 160 ℃, and discharging to obtain a finished product.
By adopting the technical scheme, the preparation method is relatively simple to operate, convenient for control production in different sections, convenient for DCS control and capable of reducing production cost.
Preferably, the second step is specifically performed by introducing nitrogen into the esterification reactor until air in the esterification reactor is replaced, heating the esterification reactor at a heating rate of 0.8 ℃/min until stearic acid is completely melted, and stirring the esterification reactor at 300-500 rpm after stearic acid is completely melted.
By adopting the technical scheme, the reaction under the protection of nitrogen reduces the probability of high-temperature yellowing, is beneficial to improving the integral chroma and color and improves the product quality.
Preferably, the third step is specifically performed by heating to 100 ℃ at a heating rate of 0.8 ℃/min, adding ethylene diamine dropwise at a rotation speed of 360rpm, maintaining the temperature of the materials in the esterification reactor at 100 ℃, and controlling the adding time of the ethylene diamine to be 40min.
By adopting the technical scheme, the dripping speed and the dripping time of the ethylenediamine are strictly controlled, and the amine value, the melting point, the color and the thermal stability of a final product can be improved.
Preferably, in the fourth step, after the dropwise addition, the temperature is raised to 130 ℃ at a constant heating rate of 0.5-0.8 ℃/min, the temperature is maintained for 1 hour, then the temperature is raised to 200 ℃ at a constant heating rate of 0.5-1.0 ℃/min, the temperature is maintained for 5 hours, and the dehydration is carried out.
By adopting the technical scheme, the esterification rate can be improved, so that the material loss is reduced, and the method is more energy-saving and environment-friendly.
In summary, the present application has the following advantages:
1. the finished product prepared in the application is not easy to yellow, has good whiteness and higher product quality.
2. The preparation method is simple, DCS control is convenient to perform, and meanwhile production cost is convenient to reduce.
Detailed Description
The present application will be described in further detail with reference to examples.
Starting materials
Examples
Example 1
The lubricant Ethylene Bis Stearamide (EBS) disclosed by the application is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 285g of 2, 6-di-tert-butyl-p-cresol and 8.55kg of ethylenediamine.
A preparation method of lubricant Ethylene Bis Stearamide (EBS) comprises the following steps:
weighing 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid and 285g of 2, 6-di-tert-butyl-p-cresol according to a ratio, and adding the stearic acid, the compound catalyst and the antioxidant which are accurately weighed into an esterification reactor;
step two, introducing nitrogen into the esterification reactor, continuously introducing for 3min, replacing air in the esterification reactor, heating at a heating speed of 0.8 ℃/min until stearic acid is completely melted, stirring at 360rpm after stearic acid is completely melted, and uniformly mixing stearic acid, the compound catalyst and the antioxidant;
step three, continuously stirring at 360rpm, heating to 100 ℃ at a heating speed of 0.8 ℃/min, dropwise adding ethylenediamine, maintaining the temperature of materials in the esterification reactor at 100 ℃, and controlling the dropwise adding time of the ethylenediamine to be 40min;
after the dripping of the ethylenediamine is finished, heating to 130 ℃ at a constant heating speed of 0.5 ℃/min, preserving heat for 1 hour, then heating to 200 ℃ at a constant heating speed of 0.5 ℃/min, preserving heat for 5 hours, and dehydrating;
and step five, sampling and analyzing, stopping the reaction when the acid value is less than 10mgKOH/g, cooling to 160 ℃, and discharging to obtain a finished product.
Example 2
Example 2 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 106.5g of phosphoric acid, 248.5g of phosphorous acid, 285g of 2, 6-di-tert-butyl-p-cresol, 8.55kg of ethylenediamine.
Example 3
Example 3 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 213g of phosphoric acid, 497g of phosphorous acid, 285g of 2, 6-di-tert-butyl-p-cresol, 8.55kg of ethylenediamine.
Example 4
Example 4 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 196g of phosphoric acid, 504g of phosphorous acid, 285g of 2, 6-di-tert-butyl-p-cresol and 8.55kg of ethylenediamine.
Example 5
Example 5 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 252g of phosphoric acid, 448g of phosphorous acid, 285g of 2, 6-di-tert-butyl-p-cresol and 8.55kg of ethylenediamine.
Example 6
Example 6 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 285g of 2, 6-di-tert-butyl-p-cresol and 8307g of ethylenediamine.
Example 7
Example 7 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 285g of 2, 6-di-tert-butyl-p-cresol and 9088g of ethylenediamine.
Example 8
Example 8 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 255g of 2, 6-di-tert-butyl-p-cresol and 8.55kg of ethylenediamine.
Example 8
Example 8 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 142g of 2, 6-di-tert-butyl-p-cresol and 8.55kg of ethylenediamine.
Example 9
Example 9 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 319.5g of 2, 6-di-tert-butyl-p-cresol and 8.55kg of ethylenediamine.
Example 10
Example 10 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 213.75g of 2, 6-di-tert-butyl-p-cresol, 71.25g of polysuccinic acid (4-hydroxy-2, 6-tetramethyl-1-piperidineethanol) ester and 8.55kg of ethylenediamine.
Example 11
Example 11 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 256.5g of 2, 6-di-tert-butyl-p-cresol, 28.5g of polysuccinic acid (4-hydroxy-2, 6-tetramethyl-1-piperidineethanol) ester and 8.55kg of ethylenediamine.
Example 12
Example 12 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 250g of 2, 6-di-tert-butyl-p-cresol, 35g of polysuccinic acid (4-hydroxy-2, 6-tetramethyl-1-piperidineethanol) ester and 8.55kg of ethylenediamine.
Example 13
Example 13 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 250.8g of n-octadecyl beta- (4-hydroxyphenyl 3, 5-di-tert-butyl) propionate, 34.2g of tris (2, 4-tert-butylphenyl) phosphite, 8.55kg of ethylenediamine.
Example 14
Example 14 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 273.6g of n-octadecyl beta- (4-hydroxyphenyl 3, 5-di-tert-butyl) propionate, 11.4g of tris (2, 4-tert-butylphenyl) phosphite, 8.55kg of ethylenediamine.
Example 15
Example 15 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 265g of n-octadecyl beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) -propionate, 20g of tris (2, 4-tert-butylphenyl) phosphite, 8.55kg of ethylenediamine.
Example 16
Example 16 differs from example 1 in that: the dropping time of ethylenediamine was controlled to 50min.
Example 17
Example 17 differs from example 1 in that: the dropping time of ethylenediamine was controlled to 60min.
Example 18
Example 18 differs from example 1 in that: after the dripping of the ethylenediamine is finished, the temperature is raised to 130 ℃ at a constant heating speed of 0.8 ℃/min, the temperature is kept for 1 hour, then the temperature is raised to 200 ℃ at a constant heating speed of 0.5 ℃/min, the temperature is kept for 5 hours, and the dehydration is carried out.
Example 19
Example 19 differs from example 1 in that: after the dropwise addition of the ethylenediamine is finished, the temperature is raised to 130 ℃ at a constant heating speed of 0.6 ℃/min, the temperature is kept for 1 hour, then the temperature is raised to 200 ℃ at a constant heating speed of 0.5 ℃/min, the temperature is kept for 5 hours, and dehydration is carried out.
Example 20
Example 20 differs from example 1 in that: after the dropwise addition of the ethylenediamine is finished, the temperature is raised to 130 ℃ at a constant heating speed of 0.6 ℃/min, the temperature is kept for 1 hour, then the temperature is raised to 200 ℃ at a constant heating speed of 1.0 ℃/min, the temperature is kept for 5 hours, and dehydration is carried out.
Example 21
Example 21 differs from example 1 in that: after the dropwise addition of the ethylenediamine is finished, the temperature is raised to 130 ℃ at a constant heating speed of 0.6 ℃/min, the temperature is kept for 1 hour, then the temperature is raised to 200 ℃ at a constant heating speed of 0.8 ℃/min, the temperature is kept for 5 hours, and dehydration is carried out.
Example 22
Example 22 differs from example 12 in that: after the dripping of the ethylenediamine is finished, heating to 130 ℃ at a constant heating speed of 0.6 ℃/min, preserving heat for 1 hour, then heating to 200 ℃ at a constant heating speed of 1.0 ℃/min, preserving heat for 5 hours, and dehydrating.
Comparative example
Comparative example 1
Comparative example 1 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 140g of phosphoric acid, 560g of phosphorous acid, 285g of 2, 6-di-tert-butyl-p-cresol and 8.55kg of ethylenediamine.
Comparative example 2
Comparative example 2 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 280g of phosphoric acid, 420g of phosphorous acid, 285g of 2, 6-di-tert-butyl-p-cresol and 8.55kg of ethylenediamine.
Comparative example 3
Comparative example 3 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 285g of 2, 6-di-tert-butyl-p-cresol and 8.0kg of ethylenediamine.
Comparative example 4
Comparative example 4 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 285g of 2, 6-di-tert-butyl-p-cresol and 9.5kg of ethylenediamine.
Comparative example 5
Comparative example 5 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 130g of 2, 6-di-tert-butyl-p-cresol and 8.55kg of ethylenediamine. .
Comparative example 6
Comparative example 6 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 340g of 2, 6-di-tert-butyl-p-cresol and 8.55kg of ethylenediamine.
Comparative example 7
Comparative example 7 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 180g of 2, 6-di-tert-butyl-p-cresol, 105g of polysuccinic acid (4-hydroxy-2, 6-tetramethyl-1-piperidineethanol) ester and 8.55kg of ethylenediamine. .
Comparative example 8
Comparative example 8 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 275g of 2, 6-di-tert-butyl-p-cresol, 10g of polysuccinic acid (4-hydroxy-2, 6-tetramethyl-1-piperidineethanol) ester and 8.55kg of ethylenediamine. .
Comparative example 9
Comparative example 9 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 230g of n-octadecyl beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) -propionate, 55g of tris (2, 4-tert-butylphenyl) phosphite, 8.55kg of ethylenediamine. .
Comparative example 10
Comparative example 10 differs from example 1 in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 210g of phosphoric acid, 490g of phosphorous acid, 280g of n-octadecyl beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) -propionate, 5g of tris (2, 4-tert-butylphenyl) phosphite, 8.55kg of ethylenediamine.
Comparative example 11
Comparative example 11 differs from example 1 in that: the dropping time of ethylenediamine was controlled to 30min.
Comparative example 12
Comparative example 12 differs from example 1 in that: the dropping time of ethylenediamine was controlled to 80min.
Comparative example 13
Comparative example 13 differs from example 1 in that: after the dripping of the ethylenediamine is finished, heating to 130 ℃ at a constant heating speed of 0.8 ℃/min, preserving heat for 1 hour, then heating to 200 ℃ at a constant heating speed of 0.5 ℃/min, preserving heat for 5 hours, and dehydrating.
Comparative example 14
Comparative example 14 example 1 differs in that: after the dripping of the ethylenediamine is finished, the temperature is raised to 130 ℃ at a constant heating speed of 1.0 ℃/min, the temperature is kept for 1 hour, then the temperature is raised to 200 ℃ at a constant heating speed of 0.5 ℃/min, the temperature is kept for 5 hours, and the dehydration is carried out. .
Comparative example 15
Comparative example 15 example 1 differs in that: after the dripping of the ethylenediamine is finished, heating to 130 ℃ at a constant heating speed of 0.6 ℃/min, preserving heat for 1 hour, then heating to 200 ℃ at a constant heating speed of 0.4 ℃/min, preserving heat for 5 hours, and dehydrating. .
Comparative example 16
Comparative example 16 example 1 differs in that: after the dropwise addition of the ethylenediamine is finished, the temperature is raised to 130 ℃ at a constant heating speed of 0.6 ℃/min, the temperature is kept for 1 hour, then the temperature is raised to 200 ℃ at a constant heating speed of 1.2 ℃/min, the temperature is kept for 5 hours, and dehydration is carried out.
Comparative example 17
Comparative example 17 example 1 differs in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 700g of phosphoric acid, 285g of 2, 6-di-tert-butyl-p-cresol and 8.55kg of ethylenediamine.
Comparative example 18
Comparative example 18 example 1 differs in that: the lubricant Ethylene Bis Stearamide (EBS) is prepared from the following raw materials in parts by weight: 71.0kg of stearic acid, 700g of phosphorous acid, 285g of 2, 6-di-tert-butyl-p-cresol and 8.55kg of ethylenediamine.
Performance test
1. For the measurement of the melting point, reference is made to GB/T8026-2014.
2. The acid number was determined according to ASTM D-1386-78, the American Standard for testing materials.
3. The amine value is determined by hydrochloric acid titration.
4. The whiteness degree is sp60 series integral sphere spectrophotometer, which refers to the whiteness degree measuring method of GBl2097-89 starch.
Detection method
Table 1 shows experimental test parameters of examples 1 to 22 and comparative examples 1 to 18
It can be seen by combining examples 1-5 and comparative examples 1-2, 17-18 and combining table 1 that the chroma of the ethylene bis stearamide prepared in example 1 is better than that of the ethylene bis stearamide prepared in examples 2-4, the chroma of the ethylene bis stearamide prepared in examples 1-5 is better than that of the ethylene bis stearamide prepared in comparative examples 1-2, and the chroma of the ethylene bis stearamide prepared in examples 1-5 is better than that of the ethylene bis stearamide prepared in comparative examples 17-18, so that the phosphoric acid and the phosphorous acid are compounded to obtain the compound catalyst, wherein the mass of the phosphoric acid in the compound catalyst accounts for 28.0-36.0% of the total mass of the compound catalyst, and the mass of the phosphorous acid accounts for 64.0-72.0% of the total mass of the compound catalyst, so as to achieve better catalytic effect and ensure the chroma of the prepared ethylene bis stearamide. By comparing the colors of the ethylene bis-stearamide in example 1 with those of the ethylene bis-stearamides in examples 2 to 4, it can be seen that the quality of the prepared ethylene bis-stearamide is the best when the ethylene bis-stearamide in example 1 is whiter, the mass of phosphoric acid accounts for 30% of the total mass of the compound catalyst, the mass of phosphorous acid accounts for 70% of the total mass of the compound catalyst, and the total mass of the compound catalyst accounts for 0.087% of the total mass of the formula.
As can be seen by combining examples 1, 6 and 7 and comparative examples 3 to 4 with Table 1, the detection index of the ethylene bis stearamide prepared in examples 1, 6 and 7 is superior to that of the ethylene bis stearamide prepared in comparative examples 3 to 4, and thus the quality of the ethylene bis stearamide prepared is better when the molar ratio of stearic acid to ethylenediamine is controlled to 1.65 to 1.80 (11.7 to 12.8 parts of ethylenediamine in the formulation). By comparing the colors of the ethylene bis-stearamide of example 1 with those of examples 6-7, it can be seen that the ethylene bis-stearamide of example 1 is whiter, and the best quality of the ethylene bis-stearamide is obtained when the molar ratio of stearic acid to ethylenediamine is controlled to 1.754 (12.04 parts of ethylenediamine in the formulation).
As can be seen by combining examples 1, 8-9 and comparative examples 5-6 with Table 1, the detection index of the ethylene bis-stearamide prepared in examples 1, 8-9 is better than that of the ethylene bis-stearamide prepared in comparative examples 5-6, and thus the quality of the prepared ethylene bis-stearamide is better when the amount of 2, 6-di-t-butyl-p-cresol is 0.2-0.45 part. By comparing the colors of the ethylene bis-stearamide of example 1 with those of examples 8-9, it was found that the ethylene bis-stearamide of example 1 was whiter and that the quality of the ethylene bis-stearamide prepared was the best when the amount of 2, 6-di-t-butyl-p-cresol was 0.40 parts.
As can be seen by combining examples 1, 10 to 12 and comparative examples 7 to 8 with Table 1, the indexes of detection of the ethylene bis-stearamide prepared in examples 1, 10 to 12 are superior to those of the ethylene bis-stearamide prepared in comparative examples 7 to 8, and therefore, when the amount of the antioxidant is 0.40 parts, the antioxidant is 2, 6-di-t-butyl-p-cresol compounded with poly (4-hydroxy-2, 6-tetramethyl-1-piperidineethanol) succinate and the amount of 2, 6-di-t-butyl-p-cresol accounts for 75 to 90% of the total mass of the antioxidant, the prepared ethylene bis-stearamide has better quality.
As can be seen by combining examples 1, 13 to 15 and comparative examples 9 to 10 with Table 1, the detection index of the ethylene bis-stearamide prepared in examples 1, 13 to 15 is better than that of the ethylene bis-stearamide prepared in comparative examples 9 to 10, and therefore, when the amount of the antioxidant is 0.40 parts and the antioxidant is a combination of n-octadecyl beta- (4-hydroxyphenyl 3, 5-di-tert-butyl) propionate and tris (2, 4-tert-butylphenyl) phosphite and the n-octadecyl beta- (4-hydroxyphenyl 3, 5-di-tert-butyl) propionate accounts for 88 to 96 percent of the total mass of the antioxidant, the quality of the prepared ethylene bis-stearamide is better.
As can be seen by combining examples 1, 16-17 and comparative examples 11-12 with Table 1, the detection index of the ethylene bis-stearamide prepared in examples 1, 16-17 is better than that of the ethylene bis-stearamide prepared in comparative examples 11-12, so that the time for adding ethylene diamine dropwise is controlled to be 40-60min, and the quality of the prepared ethylene bis-stearamide is better. By comparing the colors of the ethylene bis-stearamide of example 1 with those of examples 6-17, it can be seen that the ethylene bis-stearamide of example 1 is whiter, and the quality of the prepared ethylene bis-stearamide is best when the time for adding ethylene diamine is controlled to be 40min.
As can be seen by combining examples 18-19 and comparative examples 13-14 with Table 1, the detection index of the ethylene bis-stearamide prepared in examples 18-19 is better than that of the ethylene bis-stearamide prepared in comparative examples 13-14, so that after the ethylene diamine is dripped, the temperature is raised to 130 ℃ at a constant heating rate of 0.50-1.0 ℃/min, the temperature is maintained for 1 hour, then the temperature is raised to 200 ℃ at a constant heating rate of 0.5 ℃/min, the temperature is maintained for 5 hours, and the dehydration is carried out, so that the quality of the prepared ethylene bis-stearamide is better. Wherein, the mode of heating to 130 ℃ at a constant heating speed of 0.60 ℃/min is optimal, thereby not only ensuring the product quality, but also shortening the production period.
It can be seen by combining examples 20-21 and comparative examples 15-16 with table 1 that the detection index of the ethylene bis-stearamide prepared in examples 20-21 is better than that of the ethylene bis-stearamide prepared in comparative examples 15-16, so that after the ethylene diamine is added dropwise, the temperature is raised to 130 ℃ at a constant heating rate of 0.6 ℃/min, the temperature is maintained for 1 hour, then the temperature is raised to 200 ℃ at a constant heating rate of 0.5-1.0 ℃/min, the temperature is maintained for 5 hours, and dehydration is performed, so that the quality of the prepared ethylene bis-stearamide is better. Wherein the temperature is raised to 200 ℃ at a constant heating speed of 0.5-1.0 ℃/min, the temperature is kept for 5 hours, the dehydration mode is optimal, the product quality is ensured, and the production period can be shortened.
The embodiments of the present invention are all preferred embodiments of the present application, and the protection scope of the present application is not limited thereby, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (3)
1. A preparation method of lubricant Ethylene Bis Stearamide (EBS) is characterized by comprising the following steps: the product is prepared from the following raw materials in parts by weight: 100 parts of stearic acid, 0.5-1.0 part of compound catalyst, 0.20-0.45 part of antioxidant and 11.7-12.8 parts of ethylenediamine; the antioxidant is one or more of 2, 6-di-tert-butyl-p-cresol, 2- (2-hydroxy-3, 5-ditert-amyl-phenyl) benzotriazole, poly (4-hydroxy-2, 6-tetramethyl-1-piperidineethanol) succinate, 4' methylenebis (2, 6-di-tert-butylphenol), n-octadecyl beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) propionate and tri (2, 4-tert-butylphenyl) phosphite; the compound catalyst consists of phosphoric acid and phosphorous acid; the mass of the phosphoric acid accounts for 28.0-36.0% of the total mass of the compound catalyst, and the mass of the phosphorous acid accounts for 64.0-72.0% of the total mass of the compound catalyst; the color of the stearic acid is below 30APHA, and the stearic acid does not change color in a melting state; the content of the ethylenediamine is more than 99.8%, the color is less than 10APHA, and the turbid and discoloring phenomena are avoided; the preparation method of the lubricant Ethylene Bis Stearamide (EBS) comprises the following steps:
step one, weighing stearic acid, a compound catalyst and an antioxidant according to a ratio, and adding the stearic acid, the compound catalyst and the antioxidant which are accurately weighed into an esterification reactor;
step two, after protective gas is introduced into the esterification reactor, heating at the speed of 0.5-1.0 ℃/min until stearic acid is completely melted, and starting stirring;
introducing nitrogen into the esterification reactor until the air in the esterification reactor is replaced, heating at a heating speed of 0.8 ℃/min until the stearic acid is completely melted, and stirring at 300-500 rpm after the stearic acid is completely melted;
step three, heating to 100 ℃, and dropwise adding ethylenediamine, wherein the dropwise adding time is controlled to be 40-60min;
heating to 100 ℃ at a heating speed of 0.8 ℃/min, dropwise adding ethylenediamine at a rotating speed of 360rpm, maintaining the temperature of materials in the esterification reactor at 100 ℃, and controlling the dropwise adding time of the ethylenediamine to be 40min;
step four, after the dropwise adding is finished, heating to 130 ℃, preserving heat for 1 hour, then heating to 200 ℃, preserving heat for 4-6 hours, and dehydrating;
after the dripping is finished, heating to 130 ℃ at a constant heating speed of 0.5-0.8 ℃/min, preserving heat for 1 hour, then heating to 200 ℃ at a constant heating speed of 0.5-1.0 ℃/min, preserving heat for 5 hours, and dehydrating;
and step five, sampling and analyzing, stopping the reaction when the acid value is less than 10mgKOH/g, cooling to 160 ℃, and discharging to obtain a finished product.
2. The method for preparing the lubricant Ethylene Bis Stearamide (EBS) according to claim 1, wherein: the antioxidant consists of 2, 6-di-tert-butyl-p-cresol and poly (4-hydroxy-2, 6-tetramethyl-1-piperidine ethanol) succinate; the 2, 6-di-tert-butyl-p-cresol accounts for 75-90% of the total mass of the antioxidant.
3. The method for preparing the lubricant Ethylene Bis Stearamide (EBS) according to claim 1, wherein: the antioxidant consists of beta- (4-hydroxyphenyl 3, 5-di-tert-butyl) n-octadecyl propionate and tris (2, 4-tert-butylphenyl) phosphite; the n-octadecyl beta- (4-hydroxyphenyl 3, 5-di-tert-butyl) propionate accounts for 88-96% of the total weight of the antioxidant.
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