A method for synthesizing a cleaning dispersant

Abstract

The present invention belongs to the field of fuel additives. The present invention provides a method for synthesizing a cleaning dispersant. Polyisobutylene, phosphorus pentasulfide and sulfur powder are subjected to a sulfurization reaction to obtain a sulfurization product solution. The sulfurization product solution is subjected to a hydrolysis reaction using xylene and tap water to obtain a hydrolyzate solution. The hydrolyzate solution is subjected to extraction and esterification reactions using an extractant and pentaerythritol, respectively, to obtain the cleaning dispersant. The phosphorus content of the final product of this process is increased from the original 0.82% to 1.78%, and the yield is increased from the original 53.0% to 76.8%. Based on small-scale tests, the present invention has obtained the optimal reaction conditions through a large number of rigorous pilot tests, and is expected to be suitable for industrial production.

Description

Technical Field

[0001] The invention belongs to the field of fuel additives, and in particular relates to a method for synthesizing a detergent dispersant. Background Art

[0002] Detergents and dispersants are mainly used for fuel and lubricating oil to remove the dirt that has formed in the engine. These dirt are mainly the oxidation products of lubricating oil and the products of incomplete combustion of fuel. Most of the new detergents and dispersants developed and produced in recent years have high alkalinity, which can neutralize the oxygen-containing acids generated by oil oxidation, prevent them from further oxidation and condensation, and play an acid neutralization role. And because detergents and dispersants have the functions of cleaning, dispersing, solubilizing and neutralizing, they can prevent the accumulation and deposition of high-temperature oxidation products of fuel, effectively reduce the harm of high-temperature oxidation products of fuel, and are widely used in high-temperature fuels.

[0003] The cleaning dispersant is a mixture of polyisobutylene pentaerythritol thiophosphate and polyisobutylene pentaerythritol phosphate, that is, a macromolecular thiophosphate polyol ester. The synthesis method of the macromolecular thiophosphate polyol ester is known to be US Pat. No. 3,281,359. The synthesis method introduced in the patent is that in a reaction kettle, a proper amount of polyisobutylene is mixed with phosphorus pentasulfide, and in the presence of a small amount of active sulfur, the mixture is reacted at 149-315°C for 6 hours, and then diluted with a proper amount of mineral lubricating oil, and then at 176°C, the mixture is hydrolyzed for 10 hours by bubbling with high-pressure steam at a certain flow rate. Then, a large amount of anhydrous methanol is added and mixed evenly, and then the mixture is allowed to stand at 60°C for 6 hours to extract the inorganic phosphoric acid produced by the previous reaction, and then the lower lubricating oil layer is left as a thiophosphate solution for standby use, and the upper alcohol solution is discarded or reprocessed. Thereafter, a proper amount of the thiophosphate obtained above is taken out and esterified with polyols and a proper amount of xylene at high temperature for several hours, and a small amount of water produced is removed, and the mixture is cooled, filtered, and dried as a product.

[0004] However, the above method has the following disadvantages: the yield of the final product is low, which increases the cost and is not suitable for industrial production. In addition, according to the existing synthesis process, the product cannot meet the requirements of the acid value not greater than 2.5 mgKOH / g and the phosphorus content greater than 1.2%.

[0005] Therefore, a method for synthesizing a detergent dispersant is needed, which can reduce costs and meet indicators. Summary of the invention

[0006] In view of the shortcomings of the prior art, the present invention provides a method for synthesizing a detergent dispersant. Based on small-scale tests, a large number of strict pilot tests are conducted to obtain the optimal conditions for sulfurization, hydrolysis, and esterification, thereby reducing costs and producing products that meet the requirements of the indicators.

[0007] In order to achieve the above object, the main technical solutions adopted by the present invention include:

[0008] The present invention provides a method for synthesizing a detergent dispersant, comprising: S1, performing a sulfurization reaction on polyisobutylene, phosphorus pentasulfide and sulfur powder to obtain a sulfurization product solution; S2, using xylene and tap water to perform a hydrolysis reaction on the sulfurization product solution to obtain a hydrolyzate solution; S3, using an extractant and pentaerythritol respectively, sequentially performing extraction and esterification reactions on the hydrolyzate solution to obtain the detergent dispersant.

[0009] Furthermore, the polyisobutylene, phosphorus pentasulfide and sulfur powder are subjected to a sulfur phosphation reaction to obtain a sulfur phosphation product solution, including: S11, dewatering the polyisobutylene to obtain anhydrous polyisobutylene; S12, sequentially adding phosphorus pentasulfide and sulfur powder to the anhydrous polyisobutylene, and heating and stirring to obtain a sulfur phosphation product; S13, adding a 180# aromatic hydrocarbon solvent to the sulfur phosphation product, cooling, and obtaining a sulfur phosphation product solution.

[0010] Furthermore, the heating temperature is 180-230° C., and the heating time is 4-10 hours; preferably, the heating temperature is 200° C., and the heating time is 8 hours.

[0011] Furthermore, the method of using xylene and tap water to hydrolyze the phosphosulfide product solution to obtain a hydrolyzate solution comprises: S21, dripping tap water into the phosphosulfide product solution, and heating and refluxing the solution to obtain a hydrolyzate; and S22, cooling the solution to 80°C, and adding xylene solvent to the hydrolyzate to obtain a hydrolyzate solution.

[0012] Furthermore, the temperature of the heating reflux is 90-140° C., and the time is 2-10 hours; preferably, the temperature of the heating reflux is 120° C., and the time is 8 hours.

[0013] Furthermore, the extractant and pentaerythritol are used to extract and esterify the hydrolyzate solution in sequence to obtain the cleaning dispersant, including: S31, adding the extractant to the hydrolyzate solution, stirring and standing the solution to obtain an upper layer liquid and a lower layer liquid; S32, adding pentaerythritol to the lower layer liquid, heating and refluxing the solution to obtain a heating reflux product; S33, adding 180# aromatics to the heating reflux product to obtain the cleaning dispersant.

[0014] Furthermore, the heating reflux temperature is 180-220° C., and the time is 2-10 h; preferably, the heating reflux temperature is 200° C., and the time is 6 h.

[0015] Furthermore, the extractant is one of methanol, ethyl acetate, 60% ethanol, 95% ethanol and water.

[0016] The beneficial effect of the present invention is that, compared with the prior art, a method for synthesizing a cleaning dispersant is provided. The present invention obtains the optimal reaction conditions and reduces the cost by changing the molar ratio of polyisobutylene and phosphorus pentasulfide, the reaction temperature, the reaction time, the reaction temperature, the reaction time, the type of extractant, the reaction temperature, and the reaction time during the esterification reaction during the sulfurization reaction. The phosphorus content of the final product of this process is increased from the original 0.82% to 1.78%, and the yield is increased from the original 53.0% to 76.8%. Based on small-scale tests, the present invention has obtained the optimal reaction conditions through a large number of strict pilot tests, and is expected to be suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other embodiments can be obtained based on these drawings without paying creative work.

[0018] Figure 1 A diagram showing a method for synthesizing a detergent dispersant according to an embodiment of the present invention is shown. DETAILED DESCRIPTION

[0019] In order to better explain the present invention and facilitate understanding, the present invention is described in detail below through specific embodiments in conjunction with the accompanying drawings.

[0020] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0021] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0022] The synthesis process of the present invention is as follows Figure 1 As shown, it is mainly divided into three steps, namely, sulfur phosphation reaction, hydrolysis reaction and esterification reaction.

[0023] Example 1: Preliminary Process

[0024] Sulfurization reaction

[0025] Add 700 g of polyisobutylene with a molecular weight of 1300 to a 2000 ml four-necked bottle, install a spherical glass condenser, turn on the cooling water, stir under nitrogen protection, heat to 100°C, purge with nitrogen (10L / min) for 10 minutes to remove moisture, add 120 g of phosphorus pentasulfide and 7 g of sulfur powder, stir at 200-210°C for 6 hours under nitrogen protection, and the reaction is completed to obtain an oily sulfur phosphation product. Add 350 g of 180# aromatic solvent to the sulfur phosphation product, cool it down, and obtain a sulfur phosphation product solution.

[0026] Hydrolysis reaction

[0027] When the temperature of the flask drops below 100°C, add 40 grams of tap water from above the condenser, stir, and reflux at 100-110°C for 10 hours (add 5 grams of water every hour) until the reaction is completed, cool to 80°C, add 350 grams of xylene solvent, and obtain a hydrolyzate solution.

[0028] Esterification reaction

[0029] When the temperature of the flask drops below 70°C, add 600 g of methanol, stir, heat to 60°C, keep at 60-70°C for 6 hours, separate the upper liquid for centralized treatment, and continue the esterification reaction of the lower liquid.

[0030] Add 60g of pentaerythritol to the lower liquid, reflux at 198-202°C for 8h, and add 180# aromatic hydrocarbon to obtain a clean dispersant.

[0031] The above experiment was repeated three times, and the acid value and phosphorus content were detected and analyzed. The data are shown in Table 1.

[0032] Table 1 Phosphorus content, acid value and yield of preliminary process products

[0033] project 1# 2# 3# average value Acid value 3.35mgKOH / g 2.75mgKOH / g 3.25mgKOH / g 3.12mgKOH / g Yield 53.2％ 53.0％ 52.8％ 53.0％ Phosphorus content 0.84％ 0.78％ 0.86％ 0.82％

[0034] The above experiment shows that the product has a dark red viscous liquid appearance, while the buyer requires a black brown liquid, with a large difference in appearance and poor color. The acid value exceeds 2.5 mgKOH / g and the phosphorus content is 0.78-0.86%, which cannot meet the buyer's requirements of an acid value of no more than 2.5 mgKOH / g and a phosphorus content of more than 1.2%.

[0035] Multiple tests have verified that the product appearance can be improved by increasing the amount of catalyst sulfur. The high acid value is caused by incomplete extraction of phosphoric acid during the extraction of the semi-finished product, which can be solved by increasing the number of extractions. At the same time, the raw materials are screened and the reaction input amount is changed to further optimize the synthesis process and make the product more in line with the quality index requirements.

[0036] After multiple tests, it was found that when the extraction times were 3 or more, the acid value of the final product was less than 2.5 mgKOH / g. Therefore, the following examples all used 5 extraction times.

[0037] The main optimized processes are: the molar ratio of polyisobutylene and phosphorus pentasulfide, reaction temperature, and reaction time during the sulfurization reaction; the reaction temperature and reaction time during the hydrolysis reaction; the type of extractant, and the reaction temperature and reaction time during the esterification reaction.

[0038] Example 2: Effect of the molar ratio of polyisobutylene to phosphorus pentasulfide on the yield

[0039] In order to ensure that the polyisobutylene and phosphorus pentasulfide react completely, the feeding amounts of polyisobutylene and phosphorus pentasulfide were adjusted and 6 batches of tests were carried out.

[0040] Sulfurization reaction

[0041] Add 700 g of polyisobutylene with a molecular weight of 1300 to a 2000 ml four-necked bottle, install a spherical glass condenser, turn on the cooling water, stir under nitrogen protection, heat to 100°C, purge with nitrogen (10L / min) for 10 minutes to remove moisture, add 70 g, 80 g, 90 g, 100 g, 110 g, 120 g of phosphorus pentasulfide and 21 g of sulfur powder respectively, stir at 205°C for 6 hours under nitrogen protection, and the reaction is completed to obtain an oily sulfur phosphation product. Add 350 g of 180# aromatic solvent to the sulfur phosphation product, cool it down, and obtain a sulfur phosphation product solution.

[0042] The color of the semi-finished product after sulfur phosphating is black-brown, indicating that increasing the amount of sulfur can solve the color problem of the product. In all the following tests, the amount of sulfur is kept at 21 grams, and the amount of polyisobutylene is kept at 700 grams.

[0043] Hydrolysis reaction

[0044] When the temperature of the flask drops below 100°C, add 40 g of tap water from above the condenser, stir, and reflux at 105°C for 10 h (add 5 g of water every hour) until the reaction is completed, cool to 80°C, add 350 g of xylene solvent, and obtain a hydrolyzate solution.

[0045] Esterification reaction

[0046] When the temperature of the flask drops below 70°C, add 600 g of methanol, stir, heat to 60°C, keep at 60-70°C for 6 hours, separate the upper liquid for centralized treatment, and continue the esterification reaction of the lower liquid.

[0047] 60 g of pentaerythritol was added to the lower liquid, refluxed at 200°C for 8 h, and 180# aromatic hydrocarbon was added. The test data of 6 batches of detergent dispersant products are shown in Table 2.

[0048] Table 2 Effect of the molar ratio of polyisobutylene to phosphorus pentasulfide on the yield

[0049] project A B C D E F <![CDATA[P2S5 quality]]> 60g 70g 80g 90g 100g 120g Molar Ratio 1:0.50 1:0.59 1:0.67 1:0.75 1:0.84 1:1.00 Phosphorus content 0.66％ 0.68％ 0.76％ 0.82％ 0.80％ 0.81％ Yield 56.1％ 56.9％ 57.2％ 58.1％ 57.3％ 56.5％

[0050] As can be seen from Table 2, as the molar ratio of polyisobutylene to phosphorus pentasulfide increases, the yield also increases. When the molar ratio of polyisobutylene to phosphorus pentasulfide is 1:0.75, the yield reaches a maximum value of 58.1%, and the reaction is relatively complete. If phosphorus pentasulfide is further increased, the yield decreases instead. Therefore, the reasonable formula is D, which uses a molar ratio of polyisobutylene to phosphorus pentasulfide of 1:0.75. Therefore, in the following examples of optimizing experimental conditions, the molar ratio of polyisobutylene to phosphorus pentasulfide is 1:0.75.

[0051] Example 3: Effect of sulfur phosphating reaction temperature on yield

[0052] The temperature of the sulfur phosphating reaction was adjusted and 6 batches of tests were carried out.

[0053] Sulfurization reaction

[0054] Add 700 g of polyisobutylene with a molecular weight of 1300 to a 2000 ml four-necked bottle, install a spherical glass condenser, turn on the cooling water, stir under nitrogen protection, heat to 100°C, purge with nitrogen (10L / min) for 10 minutes to remove moisture, add 90 g of phosphorus pentasulfide and 21 g of sulfur powder, stir at 180°C, 190°C, 200°C, 210°C, 220°C, 230°C for 6 hours under nitrogen protection, and the reaction is completed to obtain an oily sulfur phosphation product. Add 350 g of 180# aromatic solvent to the sulfur phosphation product, cool it down, and obtain a sulfur phosphation product solution.

[0055] Hydrolysis reaction

[0056] When the temperature of the flask drops below 100°C, add 40 g of tap water from above the condenser, stir, and reflux at 105°C for 10 h (add 5 g of water every hour) until the reaction is completed, cool to 80°C, add 350 g of xylene solvent, and obtain a hydrolyzate solution.

[0057] Esterification reaction

[0058] When the temperature of the flask drops below 70°C, add 600 g of methanol, stir, heat to 60°C, keep at 60-70°C for 6 hours, separate the upper liquid for centralized treatment, and continue the esterification reaction of the lower liquid.

[0059] 60 g of pentaerythritol was added to the lower liquid, refluxed at 200°C for 8 h, and 180# aromatic hydrocarbon was added. The test data of 6 batches of detergent dispersant products are shown in Table 3.

[0060] Table 3 Effect of sulfur phosphating reaction temperature on yield

[0061] temperature 180℃ 190℃ 200℃ 210℃ 220℃ 230℃ Phosphorus content 0.86％ 0.56％ 0.88％ 0.81％ 0.67％ 0.66％ Yield 57.1％ 58.3％ 59.2％ 58.7％ 57.6％ 57.4％

[0062] As can be seen from Table 3, as the sulfur phosphating reaction temperature increases, the yield also increases. When the sulfur phosphating reaction temperature is 200°C, the yield reaches a maximum value of 59.2%, and the reaction is relatively complete. If the sulfur phosphating reaction temperature continues to increase, the yield decreases instead. Therefore, the sulfur phosphating reaction temperature is 200°C. In the following examples of optimizing experimental conditions, the sulfur phosphating reaction temperature is 200°C.

[0063] Example 4: Effect of sulfur phosphating reaction time on phosphorus content

[0064] The sulfur phosphating reaction time was adjusted and 7 batches of tests were carried out.

[0065] Sulfurization reaction

[0066] Add 700 g of polyisobutylene with a molecular weight of 1300 to a 2000 ml four-necked bottle, install a spherical glass condenser, turn on the cooling water, stir under nitrogen protection, heat to 100°C, purge with nitrogen (10L / min) for 10 minutes to remove moisture, add 90 g of phosphorus pentasulfide and 21 g of sulfur powder, stir at 200°C for 4h, 5h, 6h, 7h, 8h, 9h, 10h respectively under nitrogen protection, and the reaction is completed to obtain an oily sulfur phosphation product. Add 350 g of 180# aromatic solvent to the sulfur phosphation product, cool it down, and obtain a sulfur phosphation product solution.

[0067] Hydrolysis reaction

[0068] When the temperature of the flask drops below 100°C, add 40 g of tap water from above the condenser, stir, and reflux at 105°C for 10 h (add 5 g of water every hour) until the reaction is completed, cool to 80°C, add 350 g of xylene solvent, and obtain a hydrolyzate solution.

[0069] Esterification reaction

[0070] When the temperature of the flask drops below 70°C, add 600 g of methanol, stir, heat to 60°C, keep at 60-70°C for 6 hours, separate the upper liquid for centralized treatment, and continue the esterification reaction of the lower liquid.

[0071] 60 g of pentaerythritol was added to the lower liquid, refluxed at 200°C for 8 h, and 180# aromatic hydrocarbon was added. The test data of 7 batches of detergent dispersant products are shown in Table 4.

[0072] Table 4 Effect of sulfur phosphating reaction time on yield

[0073] time 4h 5h 6h 7h 8h 9h 10h Phosphorus content 0.72％ 0.88％ 0.88％ 0.78％ 0.91％ 0.81％ 0.84％ Yield 58.1％ 58.6％ 59.2％ 59.7％ 60.3％ 58.3％ 58.1％

[0074] As shown in Table 4, as the sulfur phosphating reaction time increases, the yield also increases. When the sulfur phosphating reaction time is 8 hours, the yield reaches a maximum value of 60.3%, and the reaction is relatively complete. If the sulfur phosphating reaction time is further increased, the yield will decrease instead. Therefore, the sulfur phosphating reaction time is 8 hours. In the following examples of optimizing experimental conditions, the sulfur phosphating reaction time is 8 hours.

[0075] Example 5: Effect of hydrolysis reaction temperature on yield

[0076] The hydrolysis reaction temperature was adjusted and 6 batches of tests were carried out.

[0077] Sulfurization reaction

[0078] Add 700 g of polyisobutylene with a molecular weight of 1300 to a 2000 ml four-necked bottle, install a spherical glass condenser, turn on the cooling water, stir under nitrogen protection, heat to 100°C, purge with nitrogen (10L / min) for 10 minutes to remove moisture, add 90 g of phosphorus pentasulfide and 21 g of sulfur powder, stir at 200°C for 8 hours under nitrogen protection, and the reaction is completed to obtain an oily sulfur phosphation product. Add 350 g of 180# aromatic solvent to the sulfur phosphation product, cool it down, and obtain a sulfur phosphation product solution.

[0079] Hydrolysis reaction

[0080] When the temperature of the flask drops below 100°C, add 40 g of tap water from above the condenser, stir, and reflux at 90, 100, 110, 120, 130, and 140°C for 10 h (add 5 g of water every hour) until the reaction is completed, cool to 80°C, add 350 g of xylene solvent, and obtain a hydrolyzate solution.

[0081] Esterification reaction

[0082] When the temperature of the flask drops below 70°C, add 600 g of methanol, stir, heat to 60°C, keep at 60-70°C for 6 hours, separate the upper liquid for centralized treatment, and continue the esterification reaction of the lower liquid.

[0083] 60 g of pentaerythritol was added to the lower liquid, refluxed at 200°C for 8 h, and 180# aromatic hydrocarbon was added. The test data of 6 batches of detergent dispersant products are shown in Table 5.

[0084] Table 5 Effect of hydrolysis reaction temperature on yield

[0085] temperature 90℃ 100℃ 110℃ 120℃ 130℃ 140℃ Phosphorus content 0.78％ 0.88％ 0.95％ 1.11％ 1.12％ 1.08％ Yield 58.7％ 60.1％ 60.8％ 62.2％ 62.0％ 61.3％

[0086] As shown in Table 5, as the hydrolysis reaction temperature increases, the yield also increases. When the hydrolysis reaction temperature is 120°C, the yield reaches a maximum value of 62.2%, and the reaction is relatively complete. If the hydrolysis reaction temperature continues to increase, the yield decreases instead. Therefore, the hydrolysis reaction temperature is 120°C. In the following embodiments of the optimized experimental conditions, the hydrolysis reaction temperature is 120°C.

[0087] Example 6: Effect of hydrolysis reaction time on yield

[0088] The hydrolysis reaction time was adjusted and 5 batches of tests were conducted.

[0089] Sulfurization reaction

[0090] Add 700 g of polyisobutylene with a molecular weight of 1300 to a 2000 ml four-necked bottle, install a spherical glass condenser, turn on the cooling water, stir under nitrogen protection, heat to 100°C, purge with nitrogen (10L / min) for 10 minutes to remove moisture, add 90 g of phosphorus pentasulfide and 21 g of sulfur powder, stir at 200°C for 8 hours under nitrogen protection, and the reaction is completed to obtain an oily sulfur phosphation product. Add 350 g of 180# aromatic solvent to the sulfur phosphation product, cool it down, and obtain a sulfur phosphation product solution.

[0091] Hydrolysis reaction

[0092] When the temperature of the flask drops below 100°C, add 40 g of tap water from above the condenser, stir, and reflux at 120°C for 2h, 4h, 6h, 8h, and 10h (add 5 g of water every hour) until the reaction is completed, cool to 80°C, add 350 g of xylene solvent, and obtain a hydrolyzate solution.

[0093] Esterification reaction

[0094] When the temperature of the flask drops below 70°C, add 600 g of methanol, stir, heat to 60°C, keep at 60-70°C for 6 hours, separate the upper liquid for centralized treatment, and continue the esterification reaction of the lower liquid.

[0095] 60 g of pentaerythritol was added to the lower liquid, refluxed at 200°C for 8 h, and 180# aromatic hydrocarbon was added. The test data of 5 batches of detergent dispersant products are shown in Table 6.

[0096] Table 6 Effect of hydrolysis reaction time on yield

[0097] time 2h 4h 6h 8h 10h Phosphorus content 1.05％ 1.23％ 1.27％ 1.35％ 1.11％ Yield 46.9％ 53.5％ 61.9％ 65.3％ 62.2％

[0098] As shown in Table 6, as the hydrolysis reaction time increases, the yield also increases. When the hydrolysis reaction time is 8h, the yield reaches a maximum value of 65.3%, and the reaction is relatively complete. If the hydrolysis reaction time continues to increase, the yield decreases instead. Therefore, the hydrolysis reaction time is 8h. In the following embodiments of the optimized experimental conditions, the hydrolysis reaction time is 8h.

[0099] Example 7: Effect of different types of extractants on yield

[0100] The type of extractant was adjusted and 5 batches of tests were conducted.

[0101] Add 700 g of polyisobutylene with a molecular weight of 1300 to a 2000 ml four-necked bottle, install a spherical glass condenser, turn on the cooling water, stir under nitrogen protection, heat to 100°C, purge with nitrogen (10L / min) for 10 minutes to remove moisture, add 90 g of phosphorus pentasulfide and 21 g of sulfur powder, stir at 200°C for 8 hours under nitrogen protection, and the reaction is completed to obtain an oily sulfur phosphation product. Add 350 g of 180# aromatic solvent to the sulfur phosphation product, cool it down, and obtain a sulfur phosphation product solution.

[0102] Hydrolysis reaction

[0103] When the temperature of the flask drops below 100°C, add 40 g of tap water from above the condenser, stir, and reflux at 120°C for 8 h (add 5 g of water every hour) until the reaction is completed, cool to 80°C, add 350 g of xylene solvent, and obtain a hydrolyzate solution.

[0104] Esterification reaction

[0105] When the temperature of the flask drops below 70°C, add methanol, 95% ethanol, 60% ethanol, ethyl acetate and 600 g of water respectively, stir, heat to 60°C, keep at 60-70°C for 6 hours, separate the upper liquid for centralized treatment, and continue the esterification reaction of the lower liquid.

[0106] 60 g of pentaerythritol was added to the lower liquid, refluxed at 200°C for 8 h, and 180# aromatic hydrocarbon was added. The test data of 5 batches of detergent dispersant products are shown in Table 7.

[0107] Table 7 Effect of different types of extractants on yield

[0108] Extraction agent type Methanol 95% ethanol 60% ethanol Ethyl acetate water Phosphorus content 1.35％ 1.52％ 1.59％ 1.45％ 1.09％ Yield 65.3％ 68.6％ 71.1％ 49.8％ 40.3％

[0109] As shown in Table 7, when 60% ethanol is used as the extractant, the yield and phosphorus content reach the highest. When 95% ethanol is used for extraction, the material is not easy to separate, while when directly extracted with water, the material is seriously emulsified and is not easy to separate. Using a certain proportion of ethanol-water solution can achieve better separation and extraction effect, and ethanol mainly has a demulsification effect.

[0110] Therefore, in the following examples of optimizing experimental conditions, 60% ethanol was used as the extractant.

[0111] Example 8: Effect of esterification reaction temperature on phosphorus content

[0112] The esterification reaction temperature was adjusted and 5 batches of tests were carried out.

[0113] Sulfurization reaction

[0114] Add 700 g of polyisobutylene with a molecular weight of 1300 to a 2000 ml four-necked bottle, install a spherical glass condenser, turn on the cooling water, stir under nitrogen protection, heat to 100°C, purge with nitrogen (10L / min) for 10 minutes to remove moisture, add 90 g of phosphorus pentasulfide and 21 g of sulfur powder, stir at 200°C for 8 hours under nitrogen protection, and the reaction is completed to obtain an oily sulfur phosphation product. Add 350 g of 180# aromatic solvent to the sulfur phosphation product, cool it down, and obtain a sulfur phosphation product solution.

[0115] Hydrolysis reaction

[0116] When the temperature of the flask drops below 100°C, add 40 g of tap water from above the condenser, stir, and reflux at 120°C for 8 h (add 5 g of water every hour) until the reaction is completed, cool to 80°C, add 350 g of xylene solvent, and obtain a hydrolyzate solution.

[0117] Esterification reaction

[0118] When the temperature of the flask drops below 70°C, add 600 g of 60% ethanol, stir, heat to 60°C, keep at 60-70°C for 6 hours, separate the upper liquid for centralized treatment, and continue the esterification reaction of the lower liquid.

[0119] 60 g of pentaerythritol was added to the lower liquid, and the mixture was refluxed at 180°C, 190°C, 200°C, 210°C, and 220°C for 8 h. After adding 180# aromatic hydrocarbon, the test data of 5 batches of detergent dispersant products are shown in Table 8.

[0120] Table 8 Effect of esterification reaction temperature on yield

[0121] temperature 180℃ 190℃ 200℃ 210℃ 220℃ Phosphorus content 1.38％ 1.43％ 1.59％ 1.47％ 1.31％ Yield 48.3％ 61.5％ 71.1％ 69.8％ 67.2％

[0122] As can be seen from Table 8, as the esterification reaction temperature increases, the yield also increases. When the hydrolysis reaction temperature is 200°C, the yield reaches a maximum value of 71.1%, and the reaction is relatively complete. If the esterification reaction temperature continues to increase, the yield decreases instead. Therefore, the esterification reaction temperature is 200°C. In the following examples of optimizing experimental conditions, the esterification reaction temperature is 200°C.

[0123] Example 9: Effect of esterification reaction time on phosphorus content

[0124] The esterification reaction time was adjusted and 5 batches of tests were carried out.

[0125] Sulfurization reaction

[0126] Add 700 g of polyisobutylene with a molecular weight of 1300 to a 2000 ml four-necked bottle, install a spherical glass condenser, turn on the cooling water, stir under nitrogen protection, heat to 100°C, purge with nitrogen (10L / min) for 10 minutes to remove moisture, add 90 g of phosphorus pentasulfide and 21 g of sulfur powder, stir at 200°C for 8 hours under nitrogen protection, and the reaction is completed to obtain an oily sulfur phosphation product. Add 350 g of 180# aromatic solvent to the sulfur phosphation product, cool it down, and obtain a sulfur phosphation product solution.

[0127] Hydrolysis reaction

[0128] When the temperature of the flask drops below 100°C, add 40 g of tap water from above the condenser, stir, and reflux at 120°C for 8 h (add 5 g of water every hour) until the reaction is completed, cool to 80°C, add 350 g of xylene solvent, and obtain a hydrolyzate solution.

[0129] Esterification reaction

[0130] When the temperature of the flask drops below 70°C, add 600 g of 60% ethanol, stir, heat to 60°C, keep at 60-70°C for 6 hours, separate the upper liquid for centralized treatment, and continue the esterification reaction of the lower liquid.

[0131] 60 g of pentaerythritol was added to the lower liquid, and the mixture was refluxed at 200°C for 2 h, 4 h, 6 h, 8 h, and 10 h, respectively. After adding 180# aromatic hydrocarbon, the test data of 5 batches of detergent dispersant products were obtained and are shown in Table 9.

[0132] Table 9 Effect of esterification reaction time on yield

[0133] time 2h 4h 6h 8h 10h Phosphorus content 1.23％ 1.50％ 1.78％ 1.59％ 1.51％ Yield 40.7％ 55.6％ 76.8％ 71.1％ 65.3％

[0134] It can be seen from Table 9 that as the esterification reaction time increases, the yield also increases. When the esterification reaction time is 6 hours, the yield reaches the highest value of 76.8%, and the reaction is relatively complete. If the esterification reaction time continues to increase, the yield will decrease. Therefore, the esterification reaction time is 6 hours.

[0135] The optimal reaction conditions were obtained by changing the molar ratio of polyisobutylene and phosphorus pentasulfide, reaction temperature, reaction time in the sulfurization reaction, reaction temperature, reaction time in the hydrolysis reaction, the type of extractant, and reaction temperature and reaction time in the esterification reaction.

[0136] The molar ratio of polyisobutylene to phosphorus pentasulfide is 1:0.75, the reaction temperature is 200°C, and the reaction time is 8 hours. The temperature of the hydrolysis reaction is 120°C, and the reaction time is 8 hours. The extractant of the esterification reaction is 60% ethanol, the reaction temperature is 200°C, and the reaction time is 6 hours.

[0137] The phosphorus content of the final product of this process is increased from the original 0.82% to 1.78%, and the yield is increased from the original 53.0% to 76.8%.

[0138] Optional, functionalized ionic liquid catalysts are widely used in various industries due to their advantages of easy separation, good catalytic effect and low catalyst dosage. The functionalized ionic liquid catalyst is used to catalyze the sulfur phosphating product to produce a detergent dispersant.

[0139] Preparation of immobilized ionic liquid catalysts:

[0140] The immobilized ionic liquid organic mesoporous catalyst NpmimBF4-FDU was prepared using FDU-15 and applied to the hydrolysis of propylene carbonate to catalyze the phosphosulfurization product.

[0141] Preparation of FDU-15

[0142] At 45°C, melt 1.5g of phenol, add 0.30g of 20% NaOH aqueous solution, stir magnetically at this temperature for 15 minutes, add 2.0g of 37% formaldehyde aqueous solution, raise the temperature to 80°C, let it react for 1 hour, then slowly cool to room temperature, and adjust the Ph of the system to 7.0. Vacuum dry at 45°C for 2 hours to obtain a viscous liquid, dissolve the liquid in ethanol for later use.

[0143] Measure 20 mL of ethanol into the reaction flask, then weigh 1.0 g of F 127 In a reaction bottle, stir until the system is clear, then add 5.0 g of the A-stage aldehyde resin prepolymer ethanol solution to the reaction system, stir at room temperature for 10 min, obtain a clear solution, transfer the solution to a petri dish, evaporate at room temperature for 8 h, then place the petri dish in a 100°C oven, bake at this temperature for 24 h, obtain a transparent film material, grind the material into powder, and mark it as as-made FDU-15. Under N2 protection, place as-made FDU-15 in a tube furnace and roast at 350°C for 3 h to obtain a polymer organic mesoporous material FDU-15-350. During the roasting process, the flow rate of N2 is 90 ml / min and the heating rate is 1°C / min.

[0144] Preparation of NpmimCl

[0145] Weigh 5.0 g of methylimidazole and 5.0 g of 3-chloro-1-propanol into a reaction flask, measure 15 mL of toluene, and react at 70°C for 24 h. After the reaction is completed, add a certain amount of ethyl acetate to the system, wash three times, and distill under reduced pressure to obtain the product NpmimCl.

[0146] Preparation of ionic liquid NpmimBF4

[0147] Add 3.5 g of sodium tetrafluoroborate to NpmimCl, measure 10 mL of acetonitrile, react at 70°C for 24 h, then stop the reaction, add chloroform to the reaction solvent, wash three times, and vacuum dry the solvent at 60°C to obtain the product NpmimBF4.

[0148] Preparation of FDU-CH2Cl

[0149] In a 250mL three-necked flask, add 9.0g 1,4-butanediol, 6.5g paraformaldehyde and 15mL benzene. Stir magnetically at room temperature, pass dry hydrogen chloride gas, then transfer the reactants to a round-bottom flask and wash with petroleum ether. Remove benzene and petroleum ether by rotary evaporation. Remove the residual solid by suction filtration, add 7.0g anhydrous magnesium sulfate and dry for 2h, filter to remove the solid, and collect the fraction at 103-110°C by vacuum distillation to obtain BCMB.

[0150] In a three-necked flask equipped with a stirrer and a dropping funnel, take 2.45g of FDU-15 and dissolve it in 50mL of acetone solvent, add 1.42g of anhydrous zinc chloride, and slowly drop 10.82Gbcmb. The temperature gradually rises during the dropwise addition. After the dropwise addition is completed, react at 60°C for 6 hours to obtain a black viscous liquid. Add distilled water twice the volume of the reaction liquid to the reaction liquid, let it stand overnight, remove the gel product after the supernatant, wash it with ethanol first, then with distilled water, and vacuum dry it to obtain FDU-CH2Cl.

[0151] Preparation of Immobilized Ionic Liquid Catalyst NpmimBF4-FDU

[0152] Weigh 1.5 g NpmimBF4 into a reaction flask, add 10 mL THF, 0.2 g K2CO3, stir for 2 h, then add 0.75 g 18-crown-6, 1.5 g FDU-CH2Cl, react at 70 °C under N2 protection for 24 h, filter, wash the solid four times with acetone to obtain the catalyst NpmimBF4-FDU.

[0153] Sulfurization reaction

[0154] Add 700 g of polyisobutylene with a molecular weight of 1300 to a 2000 ml four-necked bottle, install a spherical glass condenser, turn on the cooling water, stir under nitrogen protection, heat to 100°C, purge with nitrogen (10L / min) for 10 minutes to remove moisture, add 90 g of phosphorus pentasulfide and 21 g of sulfur powder, stir at 200°C for 8 hours under nitrogen protection, and the reaction is completed to obtain an oily sulfur phosphation product. Add 350 g of 180# aromatic solvent to the sulfur phosphation product, cool it down, and obtain a sulfur phosphation product solution.

[0155] Hydrolysis reaction

[0156] When the temperature of the flask drops below 100°C, add 40 g of tap water from above the condenser, and add 20 mg of catalyst NpmimBF4-FDU, stir, and reflux at 120°C for 8 h (add 5 g of water every hour) until the reaction is completed, cool to 80°C, add 350 g of xylene solvent, and obtain a hydrolyzate solution.

[0157] Esterification reaction

[0158] When the temperature of the flask drops below 70°C, add 600 g of 60% ethanol, stir, heat to 60°C, keep at 60-70°C for 6 hours, separate the upper liquid for centralized treatment, and continue the esterification reaction of the lower liquid.

[0159] Add 60 grams of pentaerythritol to the lower liquid, reflux at 200°C for 6 hours, and add 180# aromatic hydrocarbon to obtain a clean dispersant.

[0160] The above experiment was repeated 3 times, and the yield and phosphorus content were detected and analyzed. The data are shown in Table 10.

[0161] Table 10 Yield and phosphorus content of the products

[0162] project 1 2 3 average value Yield 70.1％ 70.2％ 70.3％ 70.2％ Phosphorus content 1.88％ 1.87％ 1.89％ 1.88％

[0163] It can be seen from Table 10 that the phosphorus content of the final product of this process is increased from the original 0.82% to 1.88%, and the yield is increased from the original 53.0% to 70.2%.

[0164] Optionally, the hydrolyzate is subjected to solvent-free catalysis using a superacid to generate a detergent dispersant.

[0165] Sulfurization reaction

[0166] Add 700 g of polyisobutylene with a molecular weight of 1300 to a 2000 ml four-necked bottle, install a spherical glass condenser, turn on the cooling water, stir under nitrogen protection, heat to 100°C, purge with nitrogen (10L / min) for 10 minutes to remove moisture, add 90 g of phosphorus pentasulfide and 21 g of sulfur powder, stir at 200°C for 8 hours under nitrogen protection, and the reaction is completed to obtain an oily sulfur phosphation product. Add 350 g of 180# aromatic solvent to the sulfur phosphation product, cool it down, and obtain a sulfur phosphation product solution.

[0167] Hydrolysis reaction

[0168] When the temperature of the flask drops below 100°C, add 40 g of tap water from above the condenser, stir, and reflux at 120°C for 8 h (add 5 g of water every hour) until the reaction is completed, and dry to obtain a hydrolyzate.

[0169] Preparation of catalyst

[0170] Dissolve titanium sulfate and stannous chloride in deionized water at a ratio of 3:1, add an appropriate amount of ammonia water while stirring, and adjust the pH value to 8-9. After standing in a closed container for 24 hours, filter and wash with a vacuum pump. Then dry at 110℃-120℃ for 12 hours, crush and sieve. Prepare 0.5M sulfuric acid solution and soak for 5 minutes, then filter out the sulfuric acid solution, adjust the temperature in a resistance furnace after drying, and roast at 500-600℃ for 3 hours to obtain a solid superacid catalyst.

[0171] Synthesis of detergent dispersants

[0172] 60.0g of pentaerythritol and the above hydrolyzate were placed in a 250ml three-necked flask, and 0.5% to 2.5% of a homemade solid superacid catalyst was added. The temperature was controlled at 160 to 200°C with an electric heating jacket. After heating until the solid was completely melted, the stirrer was started to react, and dehydrated with a water pump under intermittent decompression until no water was generated. After the product was cooled, the catalyst was dissolved and filtered to recover the catalyst with chloroform to obtain a crude product, which was then dissolved and washed with cold sodium bicarbonate, and then recrystallized with 95% ethanol, filtered with suction, and dried to obtain a white waxy solid. The results are shown in Table 11.

[0173] Table 11 Effect of solid superacid catalyst on phosphorus content and yield

[0174] Reaction Esterification reaction Solid superacid catalyst Yield 76.8％ 80.3％ Phosphorus content 1.78％ 1.96％

[0175] It can be seen from Table 11 that when the solid superacid catalyst is used, the phosphorus content of the final product of this process is increased from the original 0.82% to 1.96%, and the yield is increased from the original 53.0% to 80.3%.

[0176] The synthesis method has simple process, high catalytic yield, easy separation of products, regenerable and reusable catalyst, and no pollution during the synthesis process, and has good research value and industrial application prospects.

Claims

1. A method for synthesizing a detergent dispersant, characterized in that: include: S1, performing a sulfur phosphation reaction on polyisobutylene, phosphorus pentasulfide and sulfur powder to obtain a sulfur phosphation product solution, comprising: S11, performing a water removal treatment on the polyisobutylene to obtain anhydrous polyisobutylene; S12, adding phosphorus pentasulfide and sulfur powder to the anhydrous polyisobutylene in sequence, and heating and stirring the mixture to obtain a sulfurized phosphide product; The molar ratio of the polyisobutylene to phosphorus pentasulfide is 1:0.75; The heating temperature is 200°C and the heating time is 8h; S13, adding 180# aromatic hydrocarbon solvent to the phosphosulfurization product, cooling, and obtaining a phosphosulfurization product solution; S2, using xylene and tap water to hydrolyze the sulfur phosphation product solution to obtain a hydrolyzed product solution, comprising: S21, adding tap water dropwise to the sulfur phosphation product solution, and heating and refluxing the solution to obtain a hydrolyzate; The heating reflux temperature is 120°C and the time is 8h; S22, cooling to 80° C. and adding xylene solvent to the hydrolyzate to obtain a hydrolyzate solution; S3, using an extractant and pentaerythritol respectively, sequentially extracting and esterifying the hydrolyzate solution to obtain the detergent dispersant, comprising: S31, adding an extractant to the hydrolyzate solution, stirring and standing the solution to obtain an upper layer liquid and a lower layer liquid; The extractant is 60% ethanol; S32, adding pentaerythritol to the lower layer liquid, and heating and refluxing the lower layer liquid to obtain a heating and refluxing product; The heating reflux temperature is 200°C and the time is 6h; S33, adding 180# aromatic hydrocarbon to the heated reflux product to obtain the detergent dispersant.

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