Preparation method and application of phosphate salt
By using the esterification and hydrolysis reactions of the MIL-101 series metal-organic framework material catalysts, phosphate salts with high content of monophosphate are prepared, which solves the toxicity, corrosiveness and color instability problems of phosphate synthesis in the existing technology and realizes efficient and environmentally friendly production of phosphate salts.
Patent Information
- Application Number
- CN202310053482.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-02-03
- Publication Date
- 2025-09-26
- Estimated Expiration
- 2043-02-03
AI Technical Summary
Existing phosphate ester synthesis technology has problems such as high toxicity, generation of corrosive gases, complex reactions, low yields, and unstable product color, making it difficult to industrially produce high-content phosphate monoesters.
Using MIL-101 series metal-organic framework materials as catalysts, through esterification and hydrolysis reactions, combined with specific proportions of alcohol, water and phosphorus pentoxide, phosphate salts with light color and high monoester content were prepared.
The selectivity and content of phosphate monoester are improved, the catalyst can be recycled, the product is transparent in color, and the production efficiency is high, which solves the problems of difficult catalyst separation and dark product color in traditional methods.
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Figure BDA0004059343910000121
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of surfactants, and particularly relates to a preparation method and application of a phosphate salt. Background Art
[0002] Phosphate ester surfactants belong to a class of traditional anionic surfactants. These surfactants possess both anionic and nonionic properties, exhibiting excellent antistatic, wettability, and emulsifying properties. They are widely used in the textile, pharmaceutical, papermaking, leather, and cosmetics industries. Alkyl alcohol phosphates and fatty alcohol polyoxyethylene ether phosphates are the most representative examples of phosphate ester surfactants. Their synthesis processes are essentially the same: an esterification reaction between alcohols and their derivatives and a phosphatizing agent forms a mixture of phosphate monoesters, diesters, and even triesters, along with a small amount of phosphoric acid. Phosphate monoesters, defined as products with a monoester content of at least 80%, exhibit superior antistatic properties, water solubility, foaming properties, and foam stability compared to phosphate diesters and triesters. They are also less irritating to the skin than anionic surfactants such as alkyl sulfonates and sulfates, making them ideal for skin cleansing and cosmetic emulsification. Currently, common technologies for synthesizing phosphate esters include phosphorus oxychloride, phosphoric acid, phosphorus trichloride, polyphosphoric acid, and phosphorus pentoxide (P2O5). When the reaction raw materials are alkyl alcohols, alkyl alcohol phosphates are synthesized, while when the raw materials are fatty alcohol polyoxyethylene ethers, fatty alcohol polyoxyethylene ether phosphates are synthesized. However, no matter which synthesis technology is used, it is difficult to obtain high-content phosphate monoesters. Currently, most phosphate monoesters are imported from abroad. Therefore, increasing the content of phosphate monoesters in surfactants to maximize their functionality is an important and high-value-added technology.
[0003] Currently, the existing processes for phosphorus oxychloride (POCl3) are highly volatile and toxic, and the HCl produced by the reaction can corrode the reaction equipment, resulting in certain drawbacks for industrial production. The phosphorus trichloride (PTC) process produces corrosive gases during the reaction, which harms the environment. Furthermore, the complex reaction process and low yield make it difficult to commercialize. The polyphosphoric acid (POP) process can synthesize high-content monophosphate esters, but it also leaves a large amount of phosphoric acid residual in the system. The P2O5 (Phosphorus Oxychloride) process directly uses P2O5 and alcohols for esterification, which is simple to operate and easy to react. Currently, approximately 70% of phosphate esters use P2O5 as a phosphating agent. However, this reaction is highly exothermic, resulting in poor product color stability, often ranging from light yellow to dark brown. The product is also high in impurities, and the resulting product contains a large amount of monoesters, diesters, or even triesters, along with a small amount of free phosphoric acid, making it difficult to produce high-content phosphate salts. Summary of the Invention
[0004] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a preparation method and application of a phosphate salt with light color and high phosphate monoester content.
[0005] In order to achieve the above object, the technical solution adopted by the present invention is:
[0006] In a first aspect, the present invention provides a method for preparing a phosphate salt, comprising the following steps:
[0007] S1. Weigh alcohol or its derivative, water, and a catalyst, mix them evenly, and obtain material A;
[0008] S2. Weigh phosphate and phosphorus pentoxide, mix well, and obtain material B;
[0009] S3, adding the material B described in step S2 to the material A described in step S1, mixing them evenly, and performing an esterification reaction to obtain a phosphate intermediate;
[0010] S4, adding water to the phosphate intermediate of step S3 to carry out a hydrolysis reaction, adding alkali solution to adjust the pH value, mixing evenly, and filtering to obtain the phosphate salt;
[0011] In step S1, the mass ratio of the alcohol or its derivative, water and catalyst is alcohol or its derivative: water: catalyst = 1:0-0.05:0.002-0.1; the catalyst is a MIL-101 series metal-organic framework material; and the alcohol derivative is a polyoxyethylene ether of alcohol.
[0012] The inventors of the present invention have discovered that using the MIL-101 series metal-organic framework materials described herein, which contain a high number of Lewis acid sites and a porous structure, as catalysts, and pre-dispersing phosphorus pentoxide in a relatively high content of phosphate ester into a paste or emulsion with a certain degree of fluidity, not only improves the selectivity of the esterification reaction described herein for phosphate monoesters, thereby increasing the content of phosphate monoesters in the product, but also results in a lighter color for the phosphate ester salts described herein, thereby resolving the issues of darkening the product due to byproducts and localized carbonization caused by pre-dispersion using conventional organic solvents. Furthermore, the MIL-101 series metal-organic framework materials described herein are solid catalysts that can be recovered and reused by filtering after the reaction, without residue remaining in the product.
[0013] As a preferred embodiment of the preparation method of the present invention, in step S1, the alcohol or its derivative is a fatty alcohol or its derivative; the fatty alcohol derivative is a fatty alcohol polyoxyethylene ether.
[0014] As a preferred embodiment of the preparation method of the present invention, in step S1, the alcohol or its derivative is an alkyl alcohol or a fatty alcohol polyoxyethylene ether.
[0015] As a preferred embodiment of the preparation method of the present invention, in step S1, the MIL-101 series metal-organic framework material is at least one of a derivative of MIL-101(Cr), MIL-101(Fe), and MIL-101(Cr)-SO3H.
[0016] The inventors of the present invention conducted a large number of experimental studies on the types of catalysts and found that not all metal-organic framework materials can increase the content of phosphate monoester in the product. The MIL-101 series metal-organic framework materials prepared with Cr and Fe as the metal coordination centers of the present invention are used as catalysts. Compared with other metal coordination centers, the MIL-101 series metal-organic framework materials have a regular octahedral configuration and Cr and Fe as metal coordination centers, which give them a specific pore configuration and good structural stability. Not only can the selectivity of the esterification reaction of the present invention for phosphate monoester be improved, thereby increasing the content of phosphate monoester, but the MIL-101 series metal-organic framework materials of the present invention are solid catalysts that can be filtered and recovered after the reaction is completed, effectively solving the problem of difficult separation after the reaction is completed by promoting the formation of phosphate monoester by phosphotungstic acid in the traditional preparation method. The use of other types of metal-organic framework materials is not conducive to material transfer due to their structural instability or small pore size, resulting in a decrease in the content of phosphate monoester.
[0017] As a more preferred embodiment of the preparation method of the present invention, in step S1, the MIL-101 series metal-organic framework material is MIL-101(Cr)-SO3H.
[0018] The inventors of the present invention have found that by using the above-mentioned method of the present invention to splice sulfonic acid functional groups in the side chains of the MIL-101 series metal-organic framework materials, more proton acids can be provided to the catalyst as catalytic synergists, and at the same time, they work together with the porous structure of the metal-organic framework materials to provide more possibilities for the selectivity of the esterification reaction described in the present invention, promote the formation of monophosphate esters, and thus increase the content of monophosphate esters in phosphate salts.
[0019] As a preferred embodiment of the preparation method of the present invention, in step S1, the mass ratio of the alcohol or its derivative, water and catalyst is: alcohol or its derivative: water: catalyst = 1: (0.02-0.05): 0.003-0.008.
[0020] The inventors of the present invention have discovered that, using the method for preparing a phosphate ester salt of the present invention, adding a small amount of water and a catalyst during the esterification reaction can cause a portion of the phosphorus pentoxide in the system to undergo a hydrolysis reaction with water to produce phosphoric acid, thereby promoting the esterification reaction and facilitating an increase in the content of the phosphate monoester in the phosphate ester salt in the product. However, when the amount of catalyst used is relatively high, the increase in the content of the phosphate monoester is not significant, which not only increases production costs but also hinders mass transfer, thereby reducing the content of the phosphate monoester in the phosphate ester salt.
[0021] As a preferred embodiment of the preparation method of the present invention, in step S1, the mass ratio of the alcohol or its derivative, water and catalyst is: alcohol or its derivative: water: catalyst = 1:0.02:0.004-0.006.
[0022] The inventors of the present invention have found that when the mass ratio of the alcohol or its derivative, water and catalyst of the present invention is within the above range, the content of the phosphate monoester in the phosphate salt can be higher.
[0023] As a preferred embodiment of the preparation method of the present invention, in step S2, the mass ratio of the phosphate ester to phosphorus pentoxide is phosphate ester:phosphorus pentoxide=(0.8-1.2):1.
[0024] The mass ratio of the phosphate ester to phosphorus pentoxide of the present invention enables the phosphorus pentoxide to be pre-dispersed into a paste or an emulsion with a certain fluidity, thereby making the reaction product lighter in color and more transparent, and also improving production efficiency. However, when the amount of the phosphate ester is large, the pre-dispersed phosphorus pentoxide solution becomes dilute, resulting in a decrease in the production efficiency of the reaction. When the amount of the phosphate ester is small, the dispersion effect of the phosphorus pentoxide is reduced, resulting in the formation of lumpy solids, which also reduces the production efficiency of the present invention.
[0025] As a preferred embodiment of the preparation method of the present invention, in step S3, the mixing temperature is less than 55°C.
[0026] By adopting the above-mentioned mixing temperature range of the present invention, it is possible to avoid carbonization of the pre-dispersed phosphorus pentoxide during the mixing process due to high temperature, which would result in a darker color of the reaction product.
[0027] As a preferred embodiment of the preparation method of the present invention, in step S3, the temperature of the esterification reaction is 40 to 80° C., and the time of the esterification reaction is 1 to 8 hours.
[0028] As a more preferred embodiment of the preparation method of the present invention, in step S3, the temperature of the esterification reaction is 50-60° C., and the time of the esterification reaction is 3-4 hours.
[0029] As a preferred embodiment of the preparation method of the present invention, in step S4, the mass ratio of water:phosphate ester salt intermediate is water:phosphate ester salt intermediate=(0.02-0.05):1.
[0030] The inventors of the present invention have found that when the mass ratio of water to the phosphate salt intermediate in the hydrolysis reaction of the present invention is within the above range, the content of the phosphate monoester in the product can be increased.
[0031] As a preferred embodiment of the preparation method of the present invention, in step S4, the temperature of the hydrolysis reaction is 50-100° C., and the time of the hydrolysis reaction is 1-6 hours.
[0032] As a more preferred embodiment of the preparation method of the present invention, in step S4, the temperature of the hydrolysis reaction is 70-80° C., and the time of the hydrolysis reaction is 2-3 hours.
[0033] As a preferred embodiment of the preparation method of the present invention, in step S4, the alkali solution is a sodium hydroxide solution or a potassium hydroxide solution.
[0034] In a second aspect, the present invention also provides the use of the phosphate salt obtained by the above preparation method in the preparation of a surfactant.
[0035] Compared with the prior art, the present invention has the following beneficial effects:
[0036] (1) The use of the MIL-101 series metal-organic framework material containing a large number of Lewis acid sites and a porous structure as a catalyst can improve the selectivity of the esterification reaction of the present invention for phosphate monoesters. In addition, the catalyst of the present invention is a solid catalyst and can be recovered and reused by filtering after the reaction is completed, and will not remain in the product;
[0037] (2) The present invention pre-disperses phosphorus pentoxide into a paste or an emulsion with a certain fluidity by adding a specific amount of phosphate ester, thereby making the color of the reaction product lighter and more transparent, and also improving production efficiency. DETAILED DESCRIPTION
[0038] The technical solutions of the present invention are further described below in conjunction with the embodiments. Obviously, the embodiments described are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. The methods or operations used in the embodiments, unless otherwise specified, are conventional methods or routine operations in the art.
[0039] Example 1
[0040] An embodiment of the phosphate salt of the present invention.
[0041] The preparation method of the phosphate salt described in this embodiment comprises the following steps:
[0042] S1. Weigh 580 g of fatty alcohol polyoxyethylene ether (AEO-3) and 2.9 g of MIL-101(Cr)-SO3H, place them in a 1 L three-necked flask with a stirring paddle and a thermometer, and mix them evenly to obtain material A;
[0043] S2. Weigh 120 g of fatty alcohol polyoxyethylene ether phosphate (AEO-3 phosphate) and 125 g of phosphorus pentoxide, place them in a beaker and stir until they are uniformly mixed to obtain material B;
[0044] S3, adding the material B described in step S2 into three equal portions over 40 minutes to the material A described in step S1, controlling the system temperature to <55°C during the addition, mixing evenly, raising the temperature to 60°C, and carrying out an esterification reaction for 3 hours to obtain a phosphate intermediate;
[0045] S4. Add water to the phosphate intermediate described in step S3, the mass ratio of water to phosphate intermediate is 0.04:1, heat to 70°C, carry out hydrolysis reaction for 3 hours, and then add alkali solution to adjust the pH value to 7.0, the alkali solution is 115g potassium hydroxide completely dissolved in 1320g water, mix well, filter and recover the catalyst to obtain the phosphate.
[0046] Example 2
[0047] An embodiment of the phosphate salt of the present invention. The preparation method of the phosphate salt of this embodiment differs from that of Example 1 only in that step S1 comprises weighing 580 g of AEO-3, 29 g of water, and 11.6 g of MIL-101(Cr)-SO3H, placing them in a 1 L three-necked flask equipped with a stirring paddle and a thermometer, and mixing them uniformly to obtain material A. The other steps of the preparation method of the phosphate salt of this embodiment are the same as those of Example 1.
[0048] Example 3
[0049] An embodiment of the phosphate salt of the present invention. The preparation method of the phosphate salt described in this embodiment differs from that in Example 1 only in that step S1 comprises weighing 580 g of AEO-3, 11.2 g of water, and 1.74 g of MIL-101(Cr)-SO3H, placing them in a 1 L three-necked flask equipped with a stirring paddle and a thermometer, and mixing them uniformly to obtain material A. The other steps of the preparation method of the phosphate salt described in this embodiment are the same as those in Example 1.
[0050] Example 4
[0051] An embodiment of the phosphate salt of the present invention. The preparation method of the phosphate salt described in this embodiment differs from that in Example 1 only in that step S1 comprises weighing 580 g of AEO-3, 11.2 g of water, and 4.64 g of MIL-101(Cr)-SO3H, placing them in a 1 L three-necked flask equipped with a stirring paddle and a thermometer, and mixing them uniformly to obtain material A. The other steps of the preparation method of the phosphate salt described in this embodiment are the same as those in Example 1.
[0052] Example 5
[0053] An embodiment of the phosphate salt of the present invention. The preparation method of the phosphate salt described in this embodiment differs from that in Example 1 only in that step S1 comprises weighing 580 g of AEO-3, 2.32 g of water, and 3.48 g of MIL-101(Cr)-SO3H, placing them in a 1 L three-necked flask equipped with a stirring paddle and a thermometer, and mixing them uniformly to obtain material A. The other steps of the preparation method of the phosphate salt described in this embodiment are the same as those in Example 1.
[0054] Example 6
[0055] An embodiment of the phosphate salt of the present invention. The preparation method of the phosphate salt described in this embodiment differs from that in Example 1 only in that step S1 comprises weighing 580 g of AEO-3, 11.6 g of water, and 2.32 g of MIL-101(Cr)-SO3H, placing them in a 1 L three-necked flask equipped with a stirring paddle and a thermometer, and mixing them uniformly to obtain material A. The other steps of the preparation method of the phosphate salt described in this embodiment are the same as those in Example 1.
[0056] Example 7
[0057] An embodiment of the phosphate salt of the present invention. The method for preparing the phosphate salt of this embodiment differs from that of Example 1 only in that step S1 comprises weighing 580 g of AEO-3, 11.6 g of water, and 3.48 g of MIL-101(Cr)-SO3H, placing them in a 1 L three-necked flask equipped with a stirring paddle and a thermometer, and mixing them uniformly to obtain material A. The other steps of the method for preparing the phosphate salt of this embodiment are the same as those of Example 1.
[0058] Example 8
[0059] An embodiment of the phosphate salt of the present invention. The preparation method of the phosphate salt described in this embodiment differs from that in Example 1 only in that step S1 comprises weighing 580 g of AEO-3, 11.6 g of water, and 2.9 g of MIL-101(Cr)-SO3H, placing them in a 1 L three-necked flask equipped with a stirring paddle and a thermometer, and mixing them uniformly to obtain material A. The other steps of the preparation method of the phosphate salt described in this embodiment are the same as those in Example 1.
[0060] Example 9
[0061] An embodiment of the phosphate salt of the present invention. The preparation method of the phosphate salt described in this embodiment differs from that in Example 1 only in that step S1 comprises weighing 580 g of AEO-3 and 2.9 g of MIL-101(Cr), placing them in a 1 L three-necked flask equipped with a stirring paddle and a thermometer, and mixing them uniformly to obtain material A. The other steps of the preparation method of the phosphate salt described in this embodiment are the same as those in Example 1.
[0062] Example 10
[0063] An embodiment of the phosphate salt of the present invention. The preparation method of the phosphate salt described in this embodiment differs from that in Example 1 only in that step S1 comprises weighing 580 g of AEO-3 and 2.9 g of MIL-101(Fe), placing them in a 1 L three-necked flask equipped with a stirring paddle and a thermometer, and mixing them uniformly to obtain material A. The other steps of the preparation method of the phosphate salt described in this embodiment are the same as those in Example 1.
[0064] Example 11
[0065] An embodiment of the phosphate salt of the present invention. The preparation method of the phosphate salt of this embodiment comprises the following steps:
[0066] S1, weigh 580gC 12-14 Alcohol, 11.6 g of water and 2.9 g of MIL-101(Cr)-SO3H were placed in a 1 L three-necked flask with a stirring paddle and a thermometer and mixed to obtain material A;
[0067] S2, weigh 120gC 12-14 Alcohol phosphate and 125g of phosphorus pentoxide were placed in a beaker and stirred until uniformly mixed to obtain material B;
[0068] S3, adding the material B described in step S2 into three equal portions over 40 minutes to the material A described in step S1, controlling the system temperature to <55°C during the addition, mixing evenly, raising the temperature to 60°C, and carrying out an esterification reaction for 3 hours to obtain a phosphate intermediate;
[0069] S4. Add water to the phosphate intermediate described in step S3, the mass ratio of water to phosphate intermediate is 0.04:1, heat to 70°C, carry out hydrolysis reaction for 3 hours, and then add alkali solution to adjust the pH value, the alkali solution is 115g potassium hydroxide completely dissolved in 1320g water, mix well, filter and recover the catalyst to obtain the phosphate.
[0070] Example 12
[0071] An embodiment of the phosphate ester salt of the present invention. The preparation method of the phosphate ester salt described in this embodiment differs from that in Example 1 only in that step S2 is: 100 g of AEO-3 phosphate and 125 g of phosphorus pentoxide are weighed and placed in a beaker and stirred until uniformly mixed to obtain material B; the other steps of the preparation method of the phosphate ester salt described in this embodiment are the same as those in Example 1.
[0072] Example 13
[0073] An embodiment of the phosphate salt of the present invention. The method for preparing the phosphate salt of this embodiment differs from that of Example 1 only in that step S2 comprises weighing 150 g of AEO-3 phosphate and 125 g of phosphorus pentoxide in a beaker and stirring until uniformly mixed to obtain material B. The other steps of the method for preparing the phosphate salt of this embodiment are the same as those of Example 1.
[0074] Example 14
[0075] An embodiment of the phosphate salt of the present invention. The preparation method of the phosphate salt of this embodiment comprises the following steps:
[0076] S1. Weigh 450 g of AEO-3, 9 g of water, and 2.2 g of MIL-101(Cr), place them in a 1 L three-necked flask equipped with a stirring paddle and a thermometer, and mix them evenly to obtain material A;
[0077] S2. Weigh 111 g of AEO-3 phosphate and 125 g of phosphorus pentoxide in a beaker and stir until uniformly mixed to obtain material B;
[0078] S3, adding the material B described in step S2 into three equal parts over 50 minutes to the material A described in step S1, controlling the system temperature to be less than 55°C during the addition, mixing evenly, raising the temperature to 50°C, and carrying out an esterification reaction for 3 hours to obtain a phosphate intermediate;
[0079] S4. Add water to the phosphate intermediate described in step S3, the mass ratio of water to phosphate intermediate is 0.03:1, heat to 75°C, carry out hydrolysis reaction for 2 hours, and then add alkali solution to adjust the pH value, the alkali solution is 111g potassium hydroxide completely dissolved in 1310g water, mix well, filter and recover the catalyst to obtain the phosphate.
[0080] Example 15
[0081] An embodiment of the phosphate salt of the present invention. The preparation method of the phosphate salt of this embodiment comprises the following steps:
[0082] S1. Weigh 450 g of AEO-3, 9 g of water, and 2.5 g of MIL-101(Fe), place them in a 1 L three-necked flask equipped with a stirring paddle and a thermometer, and mix them evenly to obtain material A;
[0083] S2. Weigh 130 g of AEO-3 phosphate and 125 g of phosphorus pentoxide, place in a beaker and stir until mixed uniformly to obtain material B;
[0084] S3, adding the material B described in step S2 into three equal portions over 40 minutes to the material A described in step S1, controlling the system temperature to <55°C during the addition, mixing evenly, raising the temperature to 55°C, and conducting an esterification reaction for 3.5 hours to obtain a phosphate intermediate;
[0085] S4. Add water to the phosphate intermediate described in step S3, the mass ratio of water to phosphate intermediate is 0.03:1, heat to 70°C, carry out hydrolysis reaction for 2 hours, and then add alkali solution to adjust the pH value, the alkali solution is 110g potassium hydroxide completely dissolved in 1330g water, mix well, filter and recover the catalyst to obtain the phosphate.
[0086] Comparative Example 1
[0087] A comparative example of the phosphate ester salt of the present invention. The preparation method of the phosphate ester salt described in this comparative example differs from that of Example 8 only in that step S1 comprises weighing 580 g of AEO-3 and placing it in a 1 L three-necked flask equipped with a stirring paddle and a thermometer to obtain material A. The other steps of the preparation method of the phosphate ester salt described in this comparative example are the same as those of Example 8.
[0088] Comparative Example 2
[0089] A comparative example of the phosphate salt of the present invention. The preparation method of the phosphate salt in this comparative example comprises the following steps:
[0090] S1. Weigh 580 g of AEO-3 and place it in a 1 L three-necked flask equipped with a stirring paddle and a thermometer. Add 125 g of phosphorus pentoxide to the flask in three equal portions over 40 minutes, controlling the system temperature to <55°C during addition. Mix well, raise the temperature to 60°C, and carry out esterification reaction for 3 hours to obtain a phosphate intermediate.
[0091] S2. Add water to the phosphate intermediate described in step S2, the mass ratio of water to phosphate intermediate is 0.04:1, heat to 70°C, carry out hydrolysis reaction for 3 hours, and then add alkali solution to adjust the pH value, the alkali solution is 115g potassium hydroxide completely dissolved in 1320g water, mix well, filter and recover the catalyst to obtain the phosphate.
[0092] Comparative Example 3
[0093] A comparative example of the phosphate salt of the present invention. The preparation method of the phosphate salt in this comparative example comprises the following steps:
[0094] S1. Weigh 450 g of AEO-3 and place it in a 1 L three-necked flask equipped with a stirring paddle and a thermometer. Add 125 g of phosphorus pentoxide to the flask in three equal portions over 50 minutes, controlling the system temperature to <55°C during addition. Mix well, raise the temperature to 50°C, and carry out esterification reaction for 3 hours to obtain a phosphate intermediate.
[0095] S2. Add water to the phosphate intermediate described in step S1, the mass ratio of water to phosphate intermediate is 0.03:1, heat to 75°C, carry out hydrolysis reaction for 2 hours, and then add alkali solution to adjust the pH value, the alkali solution is 111g potassium hydroxide completely dissolved in 1310g water, mix well, filter and recover the catalyst to obtain the phosphate.
[0096] Comparative Example 4
[0097] A comparative example of the phosphate ester salt of the present invention. The preparation method of the phosphate ester salt described in this comparative example differs from that of Example 8 only in that step S1 comprises weighing 580 g of AEO-3, 58 g of water, and 2.9 g of MIL-101(Cr)-SO3H, placing them in a 1 L three-necked flask equipped with a stirring paddle and a thermometer, and mixing them uniformly to obtain material A. The remaining steps of the preparation method of the phosphate ester salt described in this comparative example are the same as those of Example 8.
[0098] Comparative Example 5
[0099] A comparative example of the phosphate salt of the present invention. The preparation method of the phosphate salt described in this comparative example differs from that of Example 8 only in that step S1 comprises weighing 580 g of AEO-3, 11.6 g of water, and 4.64 g of MIL-101(Cr)-SO3H, placing them in a 1 L three-necked flask equipped with a stirring paddle and a thermometer, and mixing them uniformly to obtain material A. The remaining steps of the preparation method of the phosphate salt described in this comparative example are the same as those of Example 8.
[0100] Comparative Example 6
[0101] A comparative example of the phosphate ester salt of the present invention. The preparation method of the phosphate ester salt described in this comparative example differs from that of Example 8 only in that step S1 comprises weighing 580 g of AEO-3, 11.6 g of water, and 2.9 g of MIL-101(Cu), placing them in a 1 L three-necked flask equipped with a stirring paddle and a thermometer, and mixing them uniformly to obtain material A. The remaining steps of the preparation method of the phosphate ester salt described in this comparative example are the same as those of Example 8.
[0102] Comparative Example 7
[0103] A comparative example of the phosphate ester salt of the present invention. The preparation method of the phosphate ester salt described in this comparative example differs from that of Example 8 only in that step S1 comprises weighing 580 g of AEO-3, 11.6 g of water, and 2.9 g of MIL-53(Cr), placing them in a 1 L three-necked flask equipped with a stirring paddle and a thermometer, and mixing them uniformly to obtain material A. The other steps of the preparation method of the phosphate ester salt described in this comparative example are the same as those of Example 8.
[0104] Effect Example 1
[0105] The phosphate salts prepared in Examples 1 to 15 of the present invention and Comparative Examples 1 to 7 were subjected to performance tests. The specific test methods are as follows:
[0106] (1) pH: Test in accordance with GB / T 6368. Test temperature: 25°C. Prepare a 1:10 sample solution with distilled water, mix thoroughly, and measure immediately. The arithmetic mean of two replicate measurements is expressed to one decimal place as the test result. The absolute difference between two independent test results obtained under repeatability conditions shall not exceed 0.1 pH unit, provided that the absolute difference exceeding 0.1 pH unit does not exceed 5%.
[0107] (2) Solid content: Dry the sample at (105±5)℃ for 4h. The mass fraction of the residue is the solid content.
[0108] (3) Appearance: visual inspection.
[0109] (4) Test for the content of monoester, diester and phosphoric acid: Test according to the method of “QB / T 4948-2016 Lauryl Phosphate, Raw Material for Cosmetics”.
[0110] The test results are shown in Table 1 below.
[0111] Table 1
[0112]
[0113] As can be seen from Table 1, the esterification rates of the products of Examples 1 to 15 of the present invention were all above 90%, and the mass fraction of the phosphate monoester was all above 80%. This indicates that the method for preparing phosphate ester salts of the present invention can improve the selectivity of the esterification reaction for phosphate monoesters, thereby increasing the content of phosphate monoesters in the products. Furthermore, the products prepared in Examples 1 to 15 of the present invention were all light in color, being clear, transparent liquids, which is beneficial for product applications. Among them, Example 8 had the highest esterification rate and the highest content of phosphate monoesters in the product.
[0114] Comparing Example 8 with Comparative Example 1 and Comparative Examples 6-7, the use of the specific porous MIL-101 series metal-organic framework materials of the present invention as catalysts can provide more proton acid as a catalytic synergist, which not only improves the esterification rate but also increases the selectivity of the esterification reaction for phosphate monoesters, thereby increasing the content of phosphate monoesters in the product. However, not all metal-organic framework materials can improve the selectivity of the esterification reaction for phosphate monoesters. Comparative Examples 6-7, which use other ionic centers or other types of metal-organic framework materials as catalysts, have higher esterification rates but poorer selectivity for phosphate monoesters.
[0115] Comparing Example 8 with Comparative Example 2, the addition of a small amount of water and catalyst during the esterification reaction can cause a portion of the phosphorus pentoxide in the system to undergo a hydrolysis reaction with water to generate phosphoric acid, thereby promoting the esterification reaction, resulting in a higher content of phosphoric acid monoester in the product. When the amount of catalyst is relatively large, compared with Example 8, Comparative Example 5 not only leads to an increase in production costs, but also hinders mass transfer when the amount of catalyst is relatively large, resulting in a decrease in the content of phosphoric acid monoester in the product. When the amount of water is relatively large, compared with Example 8, the esterification rate of Comparative Example 4 is relatively low, and it also affects the content of phosphoric acid monoester in the product.
[0116] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.
Claims
1. A method for preparing a phosphate salt, characterized in that: The following steps are involved: S1. Weigh alcohol or its derivative, water, and a catalyst, mix them evenly, and obtain material A; S2. Weigh phosphate and phosphorus pentoxide, mix well, and obtain material B; S3, adding the material B described in step S2 to the material A described in step S1, mixing them evenly, and performing an esterification reaction to obtain a phosphate intermediate; S4, adding water to the phosphate intermediate of step S3 to carry out a hydrolysis reaction, adding alkali solution to adjust the pH value, mixing evenly, and filtering to obtain the phosphate salt; In step S1, the mass ratio of the alcohol or its derivative, water and catalyst is alcohol or its derivative: water: catalyst = 1: (0.02-0.05): (0.003-0.008); the catalyst is a MIL-101 series metal-organic framework material; the alcohol derivative is a polyoxyethylene ether of alcohol; and the MIL-101 series metal-organic framework material is at least one of MIL-101(Cr), MIL-101(Fe), and MIL-101(Cr)-SO3H.
2. The preparation method according to claim 1, wherein In the step S1, the alcohol or its derivative is a fatty alcohol or its derivative, and the fatty alcohol derivative is a fatty alcohol polyoxyethylene ether.
3. The preparation method according to claim 2, wherein In step S1, the alcohol or its derivative is an alkyl alcohol or a fatty alcohol polyoxyethylene ether.
4. The preparation method according to claim 1, wherein In the step S1, the MIL-101 series metal-organic framework material is MIL-101(Cr)-SO3H.
5. The preparation method according to claim 1, wherein In step S1, the mass ratio of the alcohol or its derivative, water and catalyst is: alcohol or its derivative: water: catalyst = 1:0.02:0.004-0.
006.
6. The preparation method according to claim 1, wherein In the step S2, the mass ratio of the phosphate ester to phosphorus pentoxide is phosphate ester:phosphorus pentoxide=(0.8-1.2):
1.
7. The preparation method according to claim 1, wherein In the step S4, the mass ratio of water to the phosphate intermediate is water:phosphate intermediate=(0.02-0.05):1.
Citation Information
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