Production process of glycerol polyoxyethylene ether

Abstract

The invention relates to a production process of glycerol polyoxyethylene ether, which comprises the following steps: mixing glycerol and potassium hydroxide, performing nitrogen replacement twice, and performing negative pressure pumping to-0.090 Mpa or below during replacement; raising the temperature to 100-105 DEG C, and carrying out bubbling dehydration for 1 hour by utilizing nitrogen; after the temperature is increased to 120-130 DEG C, ethylene oxide is added, the temperature is gradually increased to 145-155 DEG C, and after all ethylene oxide is added, heat preservation and curing are performed under the condition of 145-155 DEG C for 13-17 min; and then cooling to 95-105 DEG C, keeping the vacuum degassing pressure of less than or equal to-0.095 MPa for 8-12 minutes, cooling to 50-60 DEG C, and adding glacial acetic acid to adjust the pH value, thereby obtaining the product. According to the production process of the glycerol polyoxyethylene ether, provided by the invention, by optimizing reaction conditions and a treatment process, the problems in the prior art are effectively solved, and the product quality and the production efficiency are improved.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a production process of glycerol polyoxyethylene ether. Background Art

[0002] As an important polymer, Polyoxyethylene Glyceryl Ether (PEG-Glyceryl Ether) is widely used in the fields of surfactants, emulsifiers, dispersants, etc. due to its excellent physical and chemical properties. With the increasing demand for high-quality surfactants in the daily chemical, pharmaceutical, printing and dyeing industries, the production process optimization of PEG-Glyceryl Ether is particularly important.

[0003] The development of glycerol polyoxyethylene ether can be traced back to the development of glycerol, fatty acids and their derivative products. In 1897, the atmospheric pressure hydrolysis method of oils was developed, and products such as glycerol and fatty acid esters came out one after another. Subsequently, around 1930, the development of polyoxyethylene nonionic surfactants further promoted the development of this field.

[0004] Glycerol polyoxyethylene ether plays an important role in many fields. With the advancement of science and technology and the continuous improvement of people's requirements for product performance, its research and application prospects will be broader. Based on this, the present invention provides a production process of glycerol polyoxyethylene ether. Summary of the invention

[0005] The purpose of the present invention is to provide a production process of glycerol polyoxyethylene ether, which effectively solves the problems existing in the prior art by optimizing reaction conditions and treatment process, and improves product quality and production efficiency.

[0006] The present invention provides a production process of glycerol polyoxyethylene ether, comprising the following steps: Mix glycerol and potassium hydroxide, replace with nitrogen twice, and reduce the negative pressure to below -0.090Mpa during replacement; heat to 100-105°C, and dehydrate by nitrogen bubbling for 1 hour; add ethylene oxide when the temperature is increased to 120-130°C, and gradually increase the temperature to 145-155°C. After all the ethylene oxide is added, keep warm and mature at 145-155°C for 13-17 minutes; then cool to 95-105°C with vacuum degassing pressure ≤-0.095MPa, keep for 8-12 minutes, cool to 50-60°C, and add glacial acetic acid to adjust the pH.

[0007] Furthermore, the weight ratio of the glycerol, potassium hydroxide, ethylene oxide and glacial acetic acid is (900-940): (1.4-1.8): (3000-3160): (1.64-1.72).

[0008] Furthermore, the addition of ethylene oxide includes four stages, namely the first stage, the second stage, the third stage and the fourth stage; wherein the weight ratio of the addition amount of ethylene oxide in the first stage, the second stage, the third stage and the fourth stage is (14-16): (28-32): (40-50): (60-68).

[0009] Furthermore, the reaction temperature of the first stage is 125-155°C.

[0010] Furthermore, the reaction temperature of the second stage, the third stage and the fourth stage is 145-155°C.

[0011] Furthermore, the reaction pressure of the first stage is no more than 0.2 MPa.

[0012] Furthermore, the reaction pressure of the second stage, the third stage and the fourth stage is not greater than 0.3 MPa.

[0013] Furthermore, the production of the glycerol polyoxyethylene ether is carried out in a reactor.

[0014] Furthermore, the reactor needs to be pretreated during the production of glycerol polyoxyethylene ether, and the pretreatment step includes first washing with water, vacuum drying for 30-40 minutes after washing, and pressurizing with nitrogen to 0.03MPa after drying.

[0015] The beneficial effects of the present invention are: 1. The production process of the present invention ensures the stability and repeatability of the reaction process by precisely controlling the reaction temperature, pressure and time, and such precise control helps to reduce the occurrence of side reactions and improve the selectivity of the main reaction, thereby obtaining a glycerol polyoxyethylene ether product with higher purity and more stable performance; 2. In the present invention, the addition of ethylene oxide raw material is divided into four stages, and the addition amount and reaction conditions of each stage are limited. This staged addition method helps ethylene oxide and glycerol to react more fully, improves the conversion rate of the product and the uniformity of molecular weight distribution; at the same time, it is also beneficial to reduce the unreacted ethylene oxide residue and further improve the purity of the product; 3. After the reaction in the present invention is completed, the pH value can be adjusted by adding glacial acetic acid to neutralize the alkaline substances produced during the reaction, making the product more stable; in addition, the appropriate pH value also helps to remove impurities in the product and improve the purity and quality of the product. DETAILED DESCRIPTION

[0016] The technical scheme of the present invention is described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work are within the scope of protection of the present invention. It should be noted that the raw materials can be obtained commercially. The present invention is further explained below with embodiments. Example

[0017] This embodiment provides a production process of glycerol polyoxyethylene ether, the steps comprising: The reactor was pretreated, and the pretreatment step included first washing with water to ensure that there was no other residual material in the reactor, vacuum drying for 35 minutes after washing, and pressurizing with nitrogen to 0.03 MPa after drying.

[0018] Turn on the vacuum pump, add glycerol and potassium hydroxide into the reactor, and start stirring after the feeding is completed; replace with nitrogen twice, and the negative pressure is reduced to below -0.090Mpa during replacement; heat to 103°C, and dehydrate by nitrogen bubbling for 1h; add ethylene oxide when the temperature is raised to 125°C; The addition of ethylene oxide includes four stages, namely the first stage, the second stage, the third stage and the fourth stage; the weight ratio of the addition amount of ethylene oxide in the first stage, the second stage, the third stage and the fourth stage is 15:30:45:64; the reaction temperature of the first stage is 140°C, and the reaction pressure of the first stage is not more than 0.2MPa; the reaction temperature of the second stage, the third stage and the fourth stage is 150°C; the reaction pressure of the second stage, the third stage and the fourth stage is not more than 0.3MPa; The temperature is gradually increased to 150°C. After all the ethylene oxide is added, it is kept at 150°C for 15 minutes. Then the temperature is lowered to 95-105°C and the vacuum degassing pressure is ≤-0.095MPa. During degassing, the circulation pump must be turned off, and the material in the circulation pump is pumped into the reactor. Only stirring and degassing are started. After maintaining for 10 minutes, the temperature is lowered to 55°C, and glacial acetic acid is added to adjust the pH.

[0019] Wherein, the weight ratio of glycerol, potassium hydroxide, ethylene oxide and glacial acetic acid is 920:1.6:3080:1.68.

[0020] The concentration of the glycerol polyoxyethylene ether product in this embodiment is 98.6%. Example

[0021] This embodiment provides a production process of glycerol polyoxyethylene ether, the steps comprising: The reactor was pretreated, and the pretreatment step included first washing with water to ensure that there was no other residual material in the reactor, vacuum drying for 30 minutes after washing, and pressurizing with nitrogen to 0.03 MPa after drying.

[0022] Turn on the vacuum pump, add glycerol and potassium hydroxide into the reactor, and start stirring after the feeding is completed; replace with nitrogen twice, and the negative pressure is pumped to below -0.090Mpa during replacement; heat to 105°C, and dehydrate by nitrogen bubbling for 1h; add ethylene oxide when the temperature is raised to 120°C; The addition of ethylene oxide includes four stages, namely the first stage, the second stage, the third stage and the fourth stage; the weight ratio of the addition amount of ethylene oxide in the first stage, the second stage, the third stage and the fourth stage is 16:28:50:60; the reaction temperature of the first stage is 155°C, and the reaction pressure of the first stage is not more than 0.2MPa; the reaction temperature of the second stage, the third stage and the fourth stage is 145°C; the reaction pressure of the second stage, the third stage and the fourth stage is not more than 0.3MPa; The temperature is gradually increased to 155°C. When all the ethylene oxide is added, it is kept at 155°C for 13 minutes. Then the temperature is lowered to 105°C and the vacuum degassing pressure is ≤-0.095MPa. During degassing, the circulation pump must be turned off, and the material in the circulation pump is pumped into the reactor. Only stirring and degassing are started. After maintaining for 8 minutes, the temperature is lowered to 60°C, and glacial acetic acid is added to adjust the pH.

[0023] Wherein, the weight ratio of the glycerol, potassium hydroxide, ethylene oxide and glacial acetic acid is 900:1.8:3000:1.72.

[0024] The concentration of the glycerol polyoxyethylene ether product in this embodiment is 98.2%. Example

[0025] This embodiment provides a production process of glycerol polyoxyethylene ether, the steps comprising: The reactor was pretreated, and the pretreatment step included first washing with water to ensure that there was no other residual material in the reactor, vacuum drying for 40 minutes after washing, and pressurizing with nitrogen to 0.03 MPa after drying.

[0026] Turn on the vacuum pump, add glycerol and potassium hydroxide into the reactor, and start stirring after the feeding is completed; replace with nitrogen twice, and the negative pressure is pumped to below -0.090Mpa during replacement; heat to 100°C, and dehydrate by nitrogen bubbling for 1h; add ethylene oxide when the temperature is raised to 130°C; The addition of ethylene oxide includes four stages, namely the first stage, the second stage, the third stage and the fourth stage; the weight ratio of the addition amount of ethylene oxide in the first stage, the second stage, the third stage and the fourth stage is 14:32:40:68; the reaction temperature of the first stage is 125°C, and the reaction pressure of the first stage is not more than 0.2MPa; the reaction temperature of the second stage, the third stage and the fourth stage is 145°C; the reaction pressure of the second stage, the third stage and the fourth stage is not more than 0.3MPa; The temperature is gradually increased to 145°C. After all the ethylene oxide is added, it is kept at 145°C for 17 minutes. Then the temperature is lowered to 95°C for vacuum degassing with a pressure of ≤-0.095MPa. During degassing, the circulation pump must be turned off, and the material in the circulation pump is pumped into the reactor. Only stirring and degassing are started. After maintaining for 12 minutes, the temperature is lowered to 50°C, and glacial acetic acid is added to adjust the pH.

[0027] Wherein, the weight ratio of glycerol, potassium hydroxide, ethylene oxide and glacial acetic acid is 940:1.4:3160:1.64.

[0028] The concentration of the glycerol polyoxyethylene ether product in this embodiment is 98.1%.

[0029] Comparative Example 1 This comparative example provides a production process of glycerol polyoxyethylene ether, the steps comprising: The reactor was pretreated, and the pretreatment step included first washing with water to ensure that there was no other residual material in the reactor, vacuum drying for 35 minutes after washing, and pressurizing with nitrogen to 0.03 MPa after drying.

[0030] Turn on the vacuum pump, add glycerol and potassium hydroxide into the reactor, and start stirring after the feeding is completed; replace with nitrogen twice, and the negative pressure is reduced to below -0.090Mpa during replacement; heat to 103°C, and dehydrate by nitrogen bubbling for 1h; add ethylene oxide when the temperature is raised to 125°C; The addition of ethylene oxide includes three stages, namely the first stage, the second stage and the third stage; the weight ratio of the addition amount of ethylene oxide in the first stage, the second stage and the third stage is 15:30:45; the reaction temperature of the first stage is 140°C, and the reaction pressure of the first stage is not more than 0.2MPa; the reaction temperature of the second stage and the third stage is 150°C; the reaction pressure of the second stage and the third stage is not more than 0.3MPa; The temperature is gradually increased to 150°C. After all the ethylene oxide is added, it is kept at 150°C for 15 minutes. Then the temperature is lowered to 95-105°C and the vacuum degassing pressure is ≤-0.095MPa. During degassing, the circulation pump must be turned off, and the material in the circulation pump is pumped into the reactor. Only stirring and degassing are started. After maintaining for 10 minutes, the temperature is lowered to 55°C, and glacial acetic acid is added to adjust the pH.

[0031] Wherein, the weight ratio of glycerol, potassium hydroxide, ethylene oxide and glacial acetic acid is 920:1.6:3080:1.68.

[0032] The concentration of the glycerol polyoxyethylene ether product in this comparative example is 97.2%.

[0033] Comparative Example 2 This comparative example provides a production process of glycerol polyoxyethylene ether, the steps comprising: The reactor was pretreated, and the pretreatment step included first washing with water to ensure that there was no other residual material in the reactor, vacuum drying for 35 minutes after washing, and pressurizing with nitrogen to 0.03 MPa after drying.

[0034] Turn on the vacuum pump, add glycerol and potassium hydroxide into the reactor, and start stirring after the feeding is completed; replace with nitrogen twice, and the negative pressure is reduced to below -0.090Mpa during replacement; heat to 103°C, and dehydrate by nitrogen bubbling for 1h; add ethylene oxide when the temperature is raised to 125°C; The addition of ethylene oxide includes two stages, namely the first stage and the second stage; the weight ratio of the addition amount of ethylene oxide in the first stage and the second stage is 15:30; the reaction temperature of the first stage is 140°C, and the reaction pressure of the first stage is not more than 0.2MPa; the reaction temperature of the second stage is 150°C; and the reaction pressure of the second stage is not more than 0.3MPa; The temperature is gradually increased to 150°C. After all the ethylene oxide is added, it is kept at 150°C for 15 minutes. Then the temperature is lowered to 95-105°C and the vacuum degassing pressure is ≤-0.095MPa. During degassing, the circulation pump must be turned off, and the material in the circulation pump is pumped into the reactor. Only stirring and degassing are started. After maintaining for 10 minutes, the temperature is lowered to 55°C, and glacial acetic acid is added to adjust the pH.

[0035] Wherein, the weight ratio of glycerol, potassium hydroxide, ethylene oxide and glacial acetic acid is 920:1.6:3080:1.68.

[0036] The concentration of the glycerol polyoxyethylene ether product in this comparative example is 95.3%.

[0037] Comparative Example 3 This comparative example provides a production process of glycerol polyoxyethylene ether, the steps comprising: The reactor was pretreated, and the pretreatment step included first washing with water to ensure that there was no other residual material in the reactor, vacuum drying for 35 minutes after washing, and pressurizing with nitrogen to 0.03 MPa after drying.

[0038] Turn on the vacuum pump, add glycerol and potassium hydroxide into the reactor, and start stirring after the feeding is completed; replace with nitrogen twice, and the negative pressure is reduced to below -0.090Mpa during replacement; heat to 103°C, and dehydrate by nitrogen bubbling for 1h; add ethylene oxide when the temperature is raised to 125°C; Wherein, after the addition of ethylene oxide, the reaction temperature is 140°C and the reaction pressure is not greater than 0.2MPa; Then the temperature is gradually increased to 150°C. After all the ethylene oxide is added, it is kept at 150°C for 15 minutes. Then the temperature is lowered to 95-105°C for vacuum degassing with a pressure of ≤-0.095MPa. During degassing, the circulation pump must be turned off, and the material in the circulation pump is pumped into the reactor. Only stirring and degassing are started. After maintaining for 10 minutes, the temperature is lowered to 55°C, and glacial acetic acid is added to adjust the pH.

[0039] Wherein, the weight ratio of glycerol, potassium hydroxide, ethylene oxide and glacial acetic acid is 920:1.6:3080:1.68.

[0040] The concentration of the glycerol polyoxyethylene ether product in this comparative example is 92.6%.

[0041] Comparative Example 4 This comparative example provides a production process of glycerol polyoxyethylene ether, the steps comprising: The reactor was pretreated, and the pretreatment step included first washing with water to ensure that there was no other residual material in the reactor, vacuum drying for 35 minutes after washing, and pressurizing with nitrogen to 0.03 MPa after drying.

[0042] Turn on the vacuum pump, add glycerol and potassium hydroxide into the reactor, and start stirring after the feeding is completed; replace with nitrogen twice, and the negative pressure is reduced to below -0.090Mpa during replacement; heat to 103°C, and dehydrate by nitrogen bubbling for 1h; add ethylene oxide when the temperature is raised to 125°C; The addition of ethylene oxide includes four stages, namely the first stage, the second stage, the third stage and the fourth stage; the weight ratio of the addition amount of ethylene oxide in the first stage, the second stage, the third stage and the fourth stage is 15:30:45:64; the reaction temperature of the first stage is 140°C, and the reaction pressure of the first stage is not more than 0.2MPa; the reaction temperature of the second stage, the third stage and the fourth stage is 150°C; the reaction pressure of the second stage, the third stage and the fourth stage is not more than 0.3MPa; The temperature is gradually increased to 170°C. After all the ethylene oxide is added, it is kept at 170°C for 15 minutes. Then the temperature is lowered to 95-105°C and the vacuum degassing pressure is ≤-0.095MPa. During degassing, the circulation pump must be turned off, and the material in the circulation pump is pumped into the reactor. Only stirring and degassing are started. After maintaining for 10 minutes, the temperature is lowered to 55°C, and glacial acetic acid is added to adjust the pH.

[0043] Wherein, the weight ratio of glycerol, potassium hydroxide, ethylene oxide and glacial acetic acid is 920:1.6:3080:1.68.

[0044] The concentration of the glycerol polyoxyethylene ether product in this comparative example is 96.5%.

[0045] Comparative Example 5 This comparative example provides a production process of glycerol polyoxyethylene ether, the steps comprising: The reactor was pretreated, and the pretreatment step included first washing with water to ensure that there was no other residual material in the reactor, vacuum drying for 35 minutes after washing, and pressurizing with nitrogen to 0.03 MPa after drying.

[0046] Turn on the vacuum pump, add glycerol and potassium hydroxide into the reactor, and start stirring after the feeding is completed; replace with nitrogen twice, and the negative pressure is reduced to below -0.090Mpa during replacement; add ethylene oxide when the temperature is raised to 125°C; The addition of ethylene oxide includes four stages, namely the first stage, the second stage, the third stage and the fourth stage; the weight ratio of the addition amount of ethylene oxide in the first stage, the second stage, the third stage and the fourth stage is 15:30:45:64; the reaction temperature of the first stage is 140°C, and the reaction pressure of the first stage is not more than 0.2MPa; the reaction temperature of the second stage, the third stage and the fourth stage is 150°C; the reaction pressure of the second stage, the third stage and the fourth stage is not more than 0.3MPa; The temperature is gradually increased to 150°C. After all the ethylene oxide is added, it is kept at 150°C for 15 minutes. Then the temperature is lowered to 95-105°C and the vacuum degassing pressure is ≤-0.095MPa. During degassing, the circulation pump must be turned off, and the material in the circulation pump is pumped into the reactor. Only stirring and degassing are started. After maintaining for 10 minutes, the temperature is lowered to 55°C, and glacial acetic acid is added to adjust the pH.

[0047] Wherein, the weight ratio of glycerol, potassium hydroxide, ethylene oxide and glacial acetic acid is 920:1.6:3080:1.68.

[0048] The concentration of the glycerol polyoxyethylene ether product in this comparative example is 95.7%.

[0049] The glycerol polyoxyethylene ether products prepared in Examples 1-3 and Comparative Examples 1-5 were placed at 40°C for 30 days. The glycerol polyoxyethylene ether products in Examples 1-3 showed no precipitation or stratification; the glycerol polyoxyethylene ether products prepared in Comparative Examples 1 and 4 changed color slightly; the glycerol polyoxyethylene ether product prepared in Comparative Example 2 showed slight precipitation; the glycerol polyoxyethylene ether products prepared in Comparative Examples 3 and 5 showed precipitation and stratification.

[0050] Finally, it should be noted that: the present invention illustrates the product and detailed preparation method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned product and detailed preparation method, that is, it does not mean that the present invention must rely on the above-mentioned product and detailed preparation method to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention and addition of auxiliary materials, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0051] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited to the specific details in the above embodiments, and the technical solution of the present invention can be subjected to a variety of simple modifications within the technical concept of the present invention. These simple modifications all belong to the protection scope of the present invention.

[0052] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0053] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A production process for glycerol polyoxyethylene ether, characterized in that the steps include: Mix glycerol and potassium hydroxide, replace with nitrogen twice, and reduce the negative pressure to below -0.090Mpa during replacement; heat to 100-105°C, and dehydrate by nitrogen bubbling for 1 hour; add ethylene oxide when the temperature is increased to 120-130°C, and gradually increase the temperature to 145-155°C. After all the ethylene oxide is added, keep warm and mature at 145-155°C for 13-17 minutes; then cool to 95-105°C with vacuum degassing pressure ≤-0.095MPa, keep for 8-12 minutes, cool to 50-60°C, and add glacial acetic acid to adjust the pH.

2. The production process of glycerol polyoxyethylene ether according to claim 1, characterized in that: The weight ratio of the glycerol, potassium hydroxide, ethylene oxide and glacial acetic acid is (900-940): (1.4-1.8): (3000-3160): (1.64-1.72).

3. A production process for glycerol polyoxyethylene ether according to claim 1, characterized in that, The addition of ethylene oxide includes four stages, namely the first stage, the second stage, the third stage and the fourth stage; wherein the weight ratio of the addition amount of ethylene oxide in the first stage, the second stage, the third stage and the fourth stage is (14-16): (28-32): (40-50): (60-68).

4. A production process for glycerol polyoxyethylene ether according to claim 3, characterized in that, The reaction temperature of the first stage is 125-155°C.

5. A production process for glycerol polyoxyethylene ether according to claim 3, characterized in that: The reaction temperature of the second stage, the third stage and the fourth stage is 145-155°C.

6. The production process of glycerol polyoxyethylene ether according to claim 3, characterized in that: The reaction pressure of the first stage is no more than 0.2 MPa.

7. The production process of glycerol polyoxyethylene ether according to claim 3, characterized in that: The reaction pressure of the second stage, the third stage and the fourth stage is not more than 0.3 MPa.

8. The production process of glycerol polyoxyethylene ether according to claim 1, characterized in that: The production of the glycerol polyoxyethylene ether is carried out in a reactor.

9. A production process for glycerol polyoxyethylene ether according to claim 8, characterized in that: The reactor needs to be pretreated during the production of glycerol polyoxyethylene ether, and the pretreatment step includes first washing with water, vacuum drying for 30-40 minutes after washing, and pressurizing with nitrogen to 0.03MPa after drying.