CN116023645A - Synthesis method of high molecular weight polyoxyethylene stearate - Google Patents
Synthesis method of high molecular weight polyoxyethylene stearate Download PDFInfo
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- CN116023645A CN116023645A CN202211553630.2A CN202211553630A CN116023645A CN 116023645 A CN116023645 A CN 116023645A CN 202211553630 A CN202211553630 A CN 202211553630A CN 116023645 A CN116023645 A CN 116023645A
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Abstract
The invention discloses a method for synthesizing high molecular weight polyoxyethylene stearate, and belongs to the technical field of high molecular compound synthesis. Adding stearic acid and a supported solid acid catalyst into a high-pressure reaction kettle, sealing the reaction kettle, starting stirring, vacuumizing, placing nitrogen, vacuumizing, heating under a vacuum condition, dehydrating, adding ethylene oxide for reaction, discharging and filtering to obtain glycol monostearate; adding glycol monostearate and alkali metal catalyst into a high-pressure reaction kettle, sealing the reaction kettle, starting stirring and vacuumizing, placing nitrogen, vacuumizing, heating and dehydrating under vacuum, adding ethylene oxide, curing, cooling, degassing, neutralizing and discharging to obtain polyoxyethylene stearate. The polyoxyethylene stearate product prepared by the method has stable quality and light color, and can effectively reduce the content of dioxane and polyethylene glycol in the polyoxyethylene stearate.
Description
Technical Field
The invention relates to the technical field of high molecular compound synthesis, in particular to a method for synthesizing high molecular weight polyoxyethylene stearate.
Background
The polyoxyethylene stearate is an important surfactant, has good emulsifying, wetting and thickening properties, and is widely applied in various fields. For example, it is used in the pharmaceutical industry as an emulsifier, solubilizer, suppository base, ointment base, as an emulsifier, detergent, softener, antistatic agent in the textile industry, emulsifying additive in the food industry, etc. Therefore, the polyoxyethylene stearate has wide industrial application prospect and great development value.
The current industrial methods for preparing polyoxyethylene stearate mainly comprise an esterification method and an ethoxylation method. The reaction end point is difficult to determine when the polyoxyethylene stearate is prepared by the esterification method, so that the prepared product has deep color and luster, and the method has complex process and higher cost. Therefore, an ethoxylation method is generally used in industry to prepare polyoxyethylene stearate. The ethoxylation method is to add stearic acid and an alkaline catalyst into a reaction kettle to react with ethylene oxide at a certain temperature to obtain polyoxyethylene stearate. The ethoxylation method has the advantages of easy control of the end point, stable product quality, good color and the like, but the polyoxyethylene stearate prepared by the method has higher dioxane and polyethylene glycol high polymer content, and the dioxane and polyethylene glycol high polymer content greatly influence the use of the product.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for synthesizing high molecular weight polyoxyethylene stearate, and the polyoxyethylene stearate product prepared by the method has stable quality and light color and can effectively reduce the content of dioxane and polyethylene glycol in the polyoxyethylene stearate.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a method for synthesizing high molecular weight polyoxyethylene stearate, which comprises the following steps:
s1, stearic acid and a supported solid acid catalyst FeCl 3 /γ-Al 2 O 3 Adding the mixture into a high-pressure reaction kettle, sealing the reaction kettle, starting stirring and vacuumizing, replacing nitrogen for a plurality of times, vacuumizing again, heating to 60-90 ℃ under the vacuum condition, dehydrating for 1-2h, adding ethylene oxide for reaction for 1-3h, discharging after the reaction is finished, and filtering to obtain glycol monostearate;
s2, adding glycol monostearate and an alkali metal catalyst into a high-pressure reaction kettle, sealing the reaction kettle, starting stirring and vacuumizing, vacuumizing after replacing nitrogen for a plurality of times, heating to 90-110 ℃ under the vacuum condition, dehydrating for 1-2h, heating to 100-140 ℃, adding ethylene oxide, curing under the internal pressure of the reaction kettle until the pressure is unchanged, cooling, degassing, neutralizing and discharging to obtain polyoxyethylene stearate.
As a preferred embodiment of the present invention, the supported solid acid catalyst FeCl 3 /γ-Al 2 O 3 The weight of the ethylene glycol monostearate is 0.05 to 0.1 percent of the theoretical weight of the ethylene glycol monostearate.
As a preferred embodiment of the present invention, the weight of the alkali metal catalyst is 0.1 to 0.2% of the theoretical weight of polyoxyethylene stearate.
As a preferred embodiment of the present invention, the alkali metal catalyst is selected from KOH, naOH, CH 3 OK or CH 3 One of ONa.
As a preferred embodiment of the present invention, the number of times of nitrogen placement in the steps S1 and S2 is 2 to 5.
As a preferred embodiment of the present invention, the molar ratio of stearic acid to ethylene oxide in the step S1 is 1:1.1.
as a preferred embodiment of the present invention, the molar ratio of ethylene glycol monostearate to ethylene oxide in the step S2 is 1:39-99.
In a preferred embodiment of the present invention, the polymerization time in the step S1 is 1 to 2 hours.
As a preferred embodiment of the present invention, the ethylene oxide is added in the step S2 within 1 to 4 hours, and the reaction pressure is maintained below 0.4 MPa.
As a preferred embodiment of the present invention, the molecular weight of the high molecular weight polyoxyethylene stearate is 2027 to 4667g/mol.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts a two-step method to prepare the polyoxyethylene stearate, and uses a supported solid acid catalyst FeCl 3 /γ-Al 2 O 3 The catalyst can directly activate epoxy monomer, the activated monomer reacts with an initiator, no moisture is generated in the process, the reaction reacts in a pore canal of the catalyst, and the epoxy monomer is effectively prevented from generating tail biting reaction, so that the content of dioxane is reduced. Therefore, the catalyst can effectively prevent the generation of dioxane and water in the reaction, so that the content of dioxane and polyethylene glycol in the product can be obviously reduced, the prepared polyoxyethylene stearate product has stable quality and light color, has good emulsifying, wetting and thickening properties, and can be widely applied to the fields of pharmacy, textile and the like.
Drawings
FIG. 1 is a photograph (60 ℃ C.) of a polyoxyethylene stearate obtained in example 6 of the present invention;
FIG. 2 is a photograph (60 ℃ C.) of a polyoxyethylene stearate obtained in comparative example 6 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments.
Example 1
A method for synthesizing high molecular weight polyoxyethylene stearate, which comprises the following steps:
s1, synthesizing glycol monostearate: 534g stearic acid and 0.32g FeCl were charged into a 2.5L autoclave 3 /γ-Al 2 O 3 The catalyst was closed, the reactor was opened with stirring and evacuated, and then the gas in the reactor was replaced with nitrogen 3 times. Heating to 90 ℃ after nitrogen placement, dropwise adding 106g of ethylene oxide, controlling the reaction temperature to 90+/-2 ℃ and the reaction pressure to 0-0.05 MPa, curing for 0.5h after adding, degassing, cooling to 60 ℃ and discharging, and filtering to remove the catalyst.
S2, synthesizing polyoxyethylene stearate 2027: firstly, 240g of glycol monostearate and 1.52g of KOH catalyst are put into a 2.5L high-pressure reaction kettle, the reaction kettle is closed, stirring is started, vacuumizing is carried out, then the gas in the kettle is replaced by nitrogen for 3 times, the temperature is raised to 140 ℃, 1280g of ethylene oxide is dropwise added, the reaction temperature is controlled to 140+/-2 ℃ and the reaction pressure is 0-0.4 MPa, curing is carried out for 0.5h after the addition, degassing is carried out, acetic acid is used for neutralization, and the temperature is reduced to 80 ℃ for discharging, thus obtaining the polyoxyethylene stearate.
Example 2
A method for synthesizing high molecular weight polyoxyethylene stearate, which comprises the following steps:
s1, synthesizing glycol monostearate: 534g stearic acid and 0.51g FeCl were charged into a 2.5L autoclave 3 /γ-Al 2 O 3 The catalyst was closed, the reactor was opened with stirring and evacuated, and then the gas in the reactor was replaced with nitrogen 3 times. Heating to 75 ℃ after nitrogen placement, dropwise adding 106g of ethylene oxide, controlling the reaction temperature to 75+/-2 ℃ and the reaction pressure to 0-0.05 MPa, and curing after addingAnd (3) degassing for 0.5h, cooling to 60 ℃ and discharging, and filtering to remove the catalyst.
S2, synthesizing polyoxyethylene stearate 2027: 240g of glycol monostearate and 2.74g of KOH catalyst are firstly put into a 2.5L high-pressure reaction kettle, the reaction kettle is closed, stirring is started, vacuumizing is carried out, then nitrogen is used for replacing gas in the kettle for 3 times, the temperature is raised to 120 ℃, 1280g of ethylene oxide is dropwise added, the reaction temperature is controlled to be 120+/-2 ℃, the reaction pressure is 0-0.4 MPa, curing is carried out for 0.5h after the reaction is finished, degassing is carried out, acetic acid is used for neutralization, and the temperature is reduced to 80 ℃ for discharging, thus obtaining the polyoxyethylene stearate.
Example 3
A method for synthesizing high molecular weight polyoxyethylene stearate, which comprises the following steps:
s1, synthesizing glycol monostearate: 534g stearic acid and 0.64g FeCl were charged into a 2.5L autoclave 3 /γ-Al 2 O 3 The catalyst was closed, the reactor was opened with stirring and evacuated, and then the gas in the reactor was replaced with nitrogen 3 times. Heating to 60 ℃ after nitrogen placement, dropwise adding 106g of ethylene oxide, controlling the reaction temperature to be 60+/-2 ℃ and the reaction pressure to be 0-0.05 MPa, curing for 0.5h after the addition, degassing, discharging, and filtering to remove the catalyst.
S2, synthesizing polyoxyethylene stearate 2027: 240g of glycol monostearate and 3.04g of KOH catalyst are firstly put into a 2.5L high-pressure reaction kettle, the reaction kettle is closed, stirring is started, vacuumizing is carried out, then nitrogen is used for replacing gas in the kettle for 3 times, the temperature is raised to 100 ℃, 1280g of ethylene oxide is dropwise added, the reaction temperature is controlled to be 100+/-2 ℃, the reaction pressure is 0-0.4 MPa, curing is carried out for 0.5h after the reaction is finished, degassing is carried out, acetic acid is used for neutralization, and the temperature is reduced to 80 ℃ for discharging, thus obtaining the polyoxyethylene stearate.
Example 4
A method for synthesizing high molecular weight polyoxyethylene stearate, which comprises the following steps:
s1, synthesizing glycol monostearate: 534g stearic acid and 0.32g FeCl were charged into a 2.5L autoclave 3 /γ-Al 2 O 3 The catalyst is closed, the reaction kettle is opened, stirring is carried out, vacuum pumping is carried out, and then nitrogen is used for replacingThe gas in the kettle is treated for 3 times. Heating to 60 ℃ after nitrogen placement, dropwise adding 106g of ethylene oxide, controlling the reaction temperature to 90 ℃, controlling the reaction pressure to 0-0.05 MPa, curing for 0.5h after adding, degassing, cooling to 60 ℃ and discharging, and filtering to remove the catalyst.
S2, synthesizing polyoxyethylene stearate 2907: firstly, 160g of glycol monostearate and 1.45g of KOH catalyst are put into a 2.5L high-pressure reaction kettle, the reaction kettle is closed, stirring is started, vacuumizing is carried out, then the gas in the kettle is replaced by nitrogen for 3 times, the temperature is raised to 140 ℃, 1293g of ethylene oxide is dropwise added, the reaction temperature is controlled to 140 ℃, the reaction pressure is 0-0.4 MPa, curing is carried out for 0.5h after the addition is finished, degassing is carried out, acetic acid is used for neutralization, and finally, the temperature is reduced to 80 ℃ for discharging, thus obtaining the polyoxyethylene stearate.
Example 5
A method for synthesizing high molecular weight polyoxyethylene stearate, which comprises the following steps:
s1, synthesizing glycol monostearate: the procedure and conditions were as in example 4.
S2, synthesizing polyoxyethylene stearate 3787: firstly, 160g of glycol monostearate and 1.89g of KOH catalyst are put into a 2.5L high-pressure reaction kettle, the reaction kettle is closed, stirring is started, vacuumizing is carried out, then the gas in the kettle is replaced by nitrogen for 3 times, the temperature is raised to 140 ℃, 1733g of ethylene oxide is dropwise added, the reaction temperature is controlled to 140 ℃, the reaction pressure is 0-0.4 MPa, curing is carried out for 0.5h after the addition is finished, degassing is carried out, acetic acid is used for neutralization, and finally, the temperature is reduced to 80 ℃ for discharging, thus obtaining the polyoxyethylene stearate.
Example 6
A method for synthesizing high molecular weight polyoxyethylene stearate, which comprises the following steps:
s1, synthesizing glycol monostearate: the procedure and conditions were as in example 4.
S2, synthesizing polyoxyethylene stearate 4667: firstly, adding 104g of glycol monostearate and 1.56g of KOH catalyst into a 2.5L high-pressure reaction kettle, sealing the reaction kettle, starting stirring, vacuumizing, replacing gas in the kettle with nitrogen for 3 times, heating to 140 ℃, dropwise adding 1452g of ethylene oxide, controlling the reaction temperature to 140 ℃, controlling the reaction pressure to 0-0.4 MPa, curing for 0.5h after the addition, degassing, neutralizing with acetic acid, and finally cooling to 80 ℃ for discharging to obtain the polyoxyethylene stearate.
The process parameters for examples 1-6 are set forth in Table 1:
table 1 process parameters of examples 1 to 6
Comparative examples 1 to 6
Comparative examples 1 to 6 differ from examples 1 to 6 in that: the supported solid catalyst FeCl in S1 of examples 1 to 6 3 /γ-Al 2 O 3 Changing into a basic metal catalyst KOH; the catalyst amount, reaction temperature and pressure were the same as in examples 1 to 6, and the other conditions were unchanged.
The process parameter pairs for comparative examples 1 to 6 are shown in Table 2:
table 2 process parameters of comparative examples 1 to 6
Comparative example 7
A method for synthesizing polyoxyethylene stearate 2027, which comprises the following steps: adding 200g of stearic acid and 1.52g of KOH catalyst into a 2.5L high-pressure reaction kettle, sealing the reaction kettle, starting stirring, vacuumizing, replacing gas in the kettle with nitrogen for 3 times, heating to 140 ℃, dropwise adding 1318g of ethylene oxide, controlling the reaction temperature to 140+/-2 ℃, controlling the reaction pressure to 0-0.4 MPa, curing for 0.5h after the addition, degassing, neutralizing with acetic acid, and cooling to 80 ℃ for discharging to obtain polyoxyethylene stearate.
Comparative examples 8 to 9
Comparative examples 8 to 9 differ from comparative example 7 in that: the reaction temperatures were 120℃and 100℃respectively, the catalyst amounts were 0.18% and 0.2% respectively, and the other conditions were the same as in comparative example 7.
Comparative example 10
A method for synthesizing polyoxyethylene stearate 2907, which comprises the following steps: firstly, 140g of stearic acid and 1.52g of KOH catalyst are put into a 2.5L high-pressure reaction kettle, the reaction kettle is closed, stirring is started, vacuumizing is carried out, then the gas in the kettle is replaced by nitrogen for 3 times, the temperature is raised to 140 ℃, 1384g of ethylene oxide is dropwise added, the reaction temperature is controlled to be 140 ℃, the reaction pressure is 0-0.4 MPa, curing is carried out for 0.5h after the addition is finished, degassing is carried out, acetic acid is used for neutralization, and finally, the temperature is reduced to 80 ℃ for discharging, thus obtaining the polyoxyethylene stearate.
Comparative example 11
A method for synthesizing polyoxyethylene stearate 2907, which comprises the following steps: firstly adding 134g of stearic acid and 1.9g of KOH catalyst into a 2.5L high-pressure reaction kettle, sealing the reaction kettle, starting stirring and vacuumizing, then replacing the gas in the kettle with nitrogen for 3 times, heating to 140 ℃, dropwise adding 1767g of ethylene oxide, controlling the reaction temperature to 140 ℃, controlling the reaction pressure to 0-0.4 MPa, curing for 0.5h after the addition, degassing, neutralizing with acetic acid, and finally cooling to 80 ℃ for discharging to obtain the polyoxyethylene stearate.
Comparative example 12
A method for synthesizing polyoxyethylene stearate 4667, which comprises the following steps: 89g of stearic acid and 1.46g of KOH catalyst are firstly put into a 2.5L high-pressure reaction kettle, the reaction kettle is closed, stirring is started, vacuumizing is carried out, then the gas in the kettle is replaced by nitrogen for 3 times, the temperature is raised to 140 ℃, 1367g of ethylene oxide is dripped, the reaction temperature is controlled to 140 ℃, the reaction pressure is controlled to be 0-0.4 MPa, the reaction is carried out for 0.5h after the reaction is finished, degassing is carried out, acetic acid is used for neutralization, and finally the temperature is reduced to 80 ℃ for discharging, thus obtaining the polyoxyethylene stearate.
The process parameter pairs for comparative examples 7 to 12 are shown in Table 3:
table 3 process parameters for comparative examples 7 to 12
| Comparative example | Catalyst amount% | Reaction temperature (DEG C) | EO mole number in product molecule |
| 7 | 0.10 | 140 | 40 |
| 8 | 0.18 | 120 | 40 |
| 9 | 0.20 | 100 | 40 |
| 10 | 0.10 | 140 | 60 |
| 11 | 0.10 | 140 | 80 |
| 12 | 0.10 | 140 | 100 |
Effect verification experiment:
the appearance, dioxane content and polymer content of the polyoxyethylene stearates obtained in examples 1 to 6 and comparative examples 1 to 12 were examined, and the results of the examination are shown in Table 4 and FIGS. 1 to 2.
Table 4 comparison of the properties of the products obtained in examples 1 to 6 and comparative examples 1 to 12
| Project | Dioxane content/ppm | Polyethylene glycol content/% |
| Example 1 | 12 | 0.6 |
| Comparative example 1 | 87 | 3.7 |
| Comparative example 7 | 153 | 6.9 |
| Example 2 | 8 | 0.5 |
| Comparative example 2 | 65 | 3.1 |
| Comparative example 8 | 129 | 5.8 |
| Example 3 | 3 | 0.4 |
| Comparative example 3 | 42 | 2.6 |
| Comparative example 9 | 95 | 4.9 |
| Example 4 | 11 | 0.7 |
| Comparative example 4 | 86 | 4.0 |
| Comparative example 10 | 162 | 7.2 |
| Example 5 | 13 | 0.9 |
| Comparative example 5 | 85 | 4.8 |
| Comparative example 11 | 149 | 7.7 |
| Example 6 | 12 | 1.0 |
| Comparative example 6 | 88 | 5.3 |
| Comparative example 12 | 151 | 8.2 |
As can be seen from table 4: the stearic acid polyoxyethylene ether prepared by the two-step method has the advantages of clear appearance (60 ℃), low dioxane content and high molecular content, and the stearic acid polyoxyethylene ether prepared at a low temperature has the advantages of clear appearance (60 ℃) and low dioxane content and high molecular content, is prepared by the two-step method, and has the advantages of clear appearance (60 ℃) and lowest dioxane content and high molecular content when the load catalyst FeCl 3/gamma-Al 2O3 is used for the first step. FIGS. 1 and 2 are the external views of the products of example 6 and comparative example 6, respectively, and it can be seen from FIGS. 1 and 2 that the supported solid acid catalyst FeCl is used 3 /γ-Al 2 O 3 The clarity of the product is greatly improved over comparative example 6, which uses a conventional basic metal catalyst KOH.
Thus, the present invention employs a two-step process with the first step using a supported catalyst FeCl 3 /γ-Al 2 O 3 The prepared stearic acid polyoxyethylene ether has qualified indexes and stable quality.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (10)
1. A method for synthesizing high molecular weight polyoxyethylene stearate is characterized in that: the method comprises the following steps:
s1, stearic acid and a supported solid acid catalyst FeCl 3 /γ-Al 2 O 3 Adding the mixture into a high-pressure reaction kettle, sealing the reaction kettle, starting stirring and vacuumizing, replacing nitrogen for a plurality of times, vacuumizing again, heating to 60-90 ℃ under the vacuum condition, dehydrating for 1-2h, adding ethylene oxide for reaction for 1-3h, discharging after the reaction is finished, and filtering to obtain glycol monostearate;
s2, adding glycol monostearate and an alkali metal catalyst into a high-pressure reaction kettle, sealing the reaction kettle, starting stirring and vacuumizing, vacuumizing after replacing nitrogen for a plurality of times, heating to 90-110 ℃ under the vacuum condition, dehydrating for 1-2h, heating to 100-140 ℃, adding ethylene oxide, curing under the internal pressure of the reaction kettle until the pressure is unchanged, cooling, degassing, neutralizing and discharging to obtain polyoxyethylene stearate.
2. The method for synthesizing high molecular weight polyoxyethylene stearate according to claim 1, wherein: the supported solid acid catalyst FeCl 3 /γ-Al 2 O 3 The weight of the ethylene glycol monostearate is 0.05 to 0.1 percent of the theoretical weight of the ethylene glycol monostearate.
3. The method for synthesizing high molecular weight polyoxyethylene stearate according to claim 1, wherein: the weight of the alkali metal catalyst is 0.1-0.2% of the theoretical weight of the polyoxyethylene stearate.
4. The method for synthesizing high molecular weight polyoxyethylene stearate according to claim 1, wherein: the alkali metal catalyst is selected from KOH, naOH, CH 3 OK or CH 3 One of ONa.
5. The method for synthesizing high molecular weight polyoxyethylene stearate according to claim 1, wherein: the times of nitrogen placement in the steps S1 and S2 are both 2-5 times.
6. The method for synthesizing high molecular weight polyoxyethylene stearate according to claim 1, wherein: the molar ratio of stearic acid to ethylene oxide in the step S1 is 1:1.1.
7. the method for synthesizing high molecular weight polyoxyethylene stearate according to claim 1, wherein: the molar ratio of glycol monostearate to ethylene oxide in the step S2 is 1:39-99.
8. The method for synthesizing high molecular weight polyoxyethylene stearate according to claim 1, wherein: the polymerization time of the step S1 is 1-2h.
9. The method for synthesizing high molecular weight polyoxyethylene stearate according to claim 1, wherein: the ethylene oxide in the step S2 is added in 1-4 h, and the reaction pressure is kept below 0.4 MPa.
10. The method for synthesizing high molecular weight polyoxyethylene stearate according to claim 1, wherein: the molecular weight of the high molecular weight polyoxyethylene stearate is 2027-4667 g/mol.
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