CN112898557B - Ethylene glycol block polyether and synthetic method thereof - Google Patents
Ethylene glycol block polyether and synthetic method thereof Download PDFInfo
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Abstract
The invention relates to ethylene glycol block polyether and a synthesis method thereof, wherein the structural general formula of the ethylene glycol block polyether is as follows:wherein a and c are the number of epoxypropane in the molecule and b is the number of ethylene oxide in the molecule; the ethylene glycol block polyether is prepared from polyethylene glycol and ethylene oxide, wherein the polyethylene glycol is prepared from a supported compound alkyl metal catalyst, ethylene glycol and ethylene oxide. The ethylene glycol block polyether has the advantages of low color, narrow molecular weight distribution and no need of post-treatment, and adopts the supported compound alkyl metal catalyst as the catalyst, wherein the catalyst is an acid catalyst, has two active centers, high catalytic activity and quick reaction time, so that the molecular weight distribution of a product is narrow, and meanwhile, the compound alkyl metal catalyst is combined with a catalytic carrier, so that the whole reaction is reacted in a pore channel of the carrier, the reaction intermediate is prevented from generating back biting reaction, the byproduct content in the product is reduced, the catalyst can be recycled, and the cost is further saved.
Description
Technical Field
The invention belongs to the technical field of polyether, and particularly relates to ethylene glycol block polyether and a synthesis method thereof.
Background
Ethylene glycol block polyether is widely used in metal working fluids and industrial cleaners due to its good lubricity and compatibility and low foaming properties. However, the applicant found that: currently, catalysts used for synthesizing ethylene glycol block polyethers mainly include alkali metal hydroxides, alkaline earth metal hydroxides, protonic acids and Lewis acids, double Metal Cyanide (DMC) catalysts, phosphazene (PZ, PZN and PZO) catalysts, and the like; although the alkali metal hydroxide catalyst (KOH, naOH) has low price and easily obtained raw materials, the catalyst has low catalytic activity, long reaction time and more byproducts, and the products prepared by the catalyst often need complex post-treatment process, and the process has long time consumption and high cost; the Lewis acid and protonic acid catalysts have high catalytic activity, small dosage and narrow distribution of the obtained products, but have harsh reaction conditions and more byproducts; alkaline earth metal hydroxide catalysts, double metal cyanide catalysts and phosphazene catalysts, although having high catalytic activity and small amounts, have high costs and are liable to remain in the product to affect the quality of the product. In recent years, supported Double Metal Cyanide (DMC) catalysts and phosphazene (PZ, PZN, and PZO) catalysts have appeared in succession in the field of polyether synthesis, but their high cost has still limited industrial applications.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the ethylene glycol block polyether which has the advantages of low color, narrow molecular weight distribution, no need of post-treatment, excellent product property, stable quality, wide application range, simple production process, low production cost, high catalytic activity of the adopted supported compound alkyl metal catalyst, quick reaction time, and effective inhibition of back biting reaction of a reaction intermediate, and catalyst recycling and use, and a synthesis method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention relates to ethylene glycol block polyether, which has a molecular structural general formula:
wherein a and c are the number of epoxypropane in the molecule and b is the number of ethylene oxide in the molecule.
Further, the ethylene glycol block polyether is prepared from polyethylene glycol and ethylene oxide, wherein the polyethylene glycol is prepared from a supported compound alkyl metal catalyst, ethylene glycol and ethylene oxide.
Further, the supported compound metal alkyl catalyst is prepared from a compound metal alkyl catalyst and a catalyst carrier, wherein the compound metal alkyl catalyst is prepared by compounding two metal alkyl catalysts.
Further, the compound alkyl metal catalyst consists of MgEt 2 And AlEt 3 Is compounded, the catalyst carrier is gamma-Al 2 O 3 。
Further, the MgEt 2 And AlEt 3 The mass ratio of (2) is 1:1-4.
The invention also provides a synthesis method of the ethylene glycol block polyether, which comprises the following steps:
(1) Preparing a supported compound metal alkyl catalyst, namely compounding two metal alkyl catalysts into a compound metal alkyl catalyst, and then supporting the compound metal alkyl catalyst on a catalyst carrier to obtain the supported compound metal alkyl catalyst;
(2) Preparing polyethylene glycol, namely adding a supported compound alkyl metal catalyst into the polyethylene glycol serving as a raw material, adding ethylene oxide into the mixture to perform polymerization reaction to obtain polyethylene glycol, and performing vacuum degassing after the reaction is finished;
(3) Preparing ethylene glycol block polyether, namely adding propylene oxide into polyethylene glycol serving as a raw material for polymerization reaction, and degassing and filtering after the reaction is finished to obtain the ethylene glycol block polyether.
Further, the specific steps for preparing polyethylene glycol are as follows: firstly adding ethylene glycol and a supported compound alkyl metal catalyst into a high-pressure reaction kettle, vacuumizing after sealing the reaction kettle, then purging with nitrogen, repeatedly placing nitrogen for a plurality of times, heating, adding ethylene oxide, curing until the pressure is almost unchanged under the internal pressure of the reaction kettle, and finally cooling, degassing and discharging; the number of times of repeatedly placing nitrogen is preferably 3, and then the temperature is preferably increased to 120 ℃, preferably after 60 minutes of ethylene oxide is added, the internal pressure of the reaction kettle is preferably kept below 0.2MPa, preferably the temperature is reduced to 100 ℃, and then the degassing is carried out;
the specific steps for preparing the ethylene glycol block polyether are as follows: firstly adding polyethylene glycol into a reaction kettle, repeatedly placing nitrogen for a plurality of times, then heating, adding propylene oxide, curing until the pressure is almost unchanged under the internal pressure of the reaction kettle, and finally cooling, degassing and discharging; the number of times of repeated nitrogen placement is preferably 3, propylene oxide is preferably dropwise added after the temperature is raised to 115 ℃, and the degassing is preferably carried out after the propylene oxide is dropwise added for 3-4 hours, the internal pressure of the reaction kettle is preferably kept below 0.35MPa, and the temperature is preferably lowered to 100 ℃.
Further, the catalyst carrier is subjected to washing, filtering, drying and calcining pretreatment in sequence before the supported compound alkyl metal catalyst is prepared.
Further, in the step (2), the addition amount of the supported compound alkyl metal catalyst is 0.02% -0.04% of the total mass of the polyethylene glycol.
Further, in the step (3), the addition amount of the supported compound alkyl metal catalyst is 0.02-0.04% of the total mass of the glycol block polyether.
The invention has the following advantages:
the ethylene glycol block polyether has the advantages of low color, narrow molecular weight distribution and no need of post-treatment, so that the production process is simple, the production cost is low, the supported compound alkyl metal catalyst is used as a catalyst, the catalyst is an acid catalyst and has two active centers, compared with KOH, the catalyst has high catalytic activity and quick reaction time, the molecular weight distribution of a product is narrow, and meanwhile, the compound alkyl metal catalyst is combined with a catalytic carrier, so that the whole reaction is reacted in a pore channel of the carrier, the reaction intermediate is prevented from generating a back biting reaction, the byproduct content in the product is reduced, the catalyst can be recycled, and the cost is further saved.
Drawings
FIG. 1 is a schematic flow chart of a process for synthesizing ethylene glycol block polyether according to the present invention;
FIG. 2 is a graph of differential refractive signals of an ethylene glycol block polyether according to the present invention;
FIG. 3 is a 13C nuclear magnetic resonance spectrum of the ethylene glycol block polyether of the present invention;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the ethylene glycol block polyether in the examples of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention relates to ethylene glycol block polyether, which has a molecular structural general formula:
wherein a and c are the number of epoxypropane (PO) in the molecule and b is the number of Ethylene Oxide (EO) in the molecule.
The ethylene glycol block polyether is prepared from polyethylene glycol and ethylene oxide, wherein the polyethylene glycol is prepared from a supported compound alkyl metal catalyst, ethylene glycol and ethylene oxide; the supported compound metal alkyl catalyst is prepared from compound metal alkyl catalysts and catalyst carriers, wherein the compound metal alkyl catalysts are prepared by compounding two metal alkyl catalysts, and the preferable scheme is as follows: the compound alkyl metal catalyst is prepared from MgEt 2 And AlEt 3 Is compounded to form the MgEt 2 And AlEt 3 The mass ratio of the catalyst carrier is preferably 1:1-4, and the catalyst carrier is gamma-Al 2 O 3 。
As shown in fig. 1, the synthesis method of the ethylene glycol block polyether comprises the following steps:
s100, preparing a supported compound metal alkyl catalyst, namely firstly compounding two metal alkyl catalysts into a compound metal alkyl catalyst, and then supporting the compound metal alkyl catalyst on a catalyst carrier to obtain the supported compound metal alkyl catalyst.
S200, preparing polyethylene glycol, namely firstly taking ethylene glycol as a raw material, adding a supported compound alkyl metal catalyst, then adding ethylene oxide for polymerization reaction to obtain polyethylene glycol, and carrying out vacuum degassing after the reaction is finished; the specific steps can be as follows: firstly adding ethylene glycol and a supported compound alkyl metal catalyst into a high-pressure reaction kettle, vacuumizing after sealing the reaction kettle, then purging with nitrogen, repeatedly placing nitrogen for a plurality of times, heating, adding ethylene oxide, curing until the pressure is almost unchanged under the internal pressure of the reaction kettle, and finally cooling, degassing and discharging; wherein the number of times of repeated nitrogen placement is preferably 3, and then the temperature is preferably increased to 120 ℃, preferably after 60 minutes of ethylene oxide is added, the internal pressure of the reaction kettle is preferably kept below 0.2MPa, preferably the temperature is reduced to 100 ℃, and then the degassing is carried out; the addition amount of the supported compound alkyl metal catalyst is preferably 0.02-0.04% of the total mass of the polyethylene glycol.
S300, preparing ethylene glycol block polyether, namely adding propylene oxide into polyethylene glycol serving as a raw material for polymerization reaction, and degassing and filtering after the reaction is finished to obtain the ethylene glycol block polyether; the specific steps can be as follows: firstly adding polyethylene glycol into a reaction kettle, repeatedly placing nitrogen for a plurality of times, then heating, adding propylene oxide, curing until the pressure is almost unchanged under the internal pressure of the reaction kettle, and finally cooling, degassing and discharging; wherein the number of times of repeatedly placing nitrogen is preferably 3, propylene oxide is dropwise added after the temperature is preferably increased to 115 ℃, and the degassing is preferably carried out after the propylene oxide is dropwise added for 3-4 hours, the internal pressure of the reaction kettle is preferably kept below 0.35MPa, and the temperature is preferably reduced to 100 ℃; the addition amount of the supported compound alkyl metal catalyst is 0.02-0.04% of the total mass of the glycol block polyether (namely, when the step 300 is executed, if the amount of the supported compound alkyl metal catalyst remained in the reaction kettle is smaller than 0.02-0.04% of the total mass of the glycol block polyether, the supported compound alkyl metal catalyst needs to be added into the reaction kettle in a supplementary mode, for example, 1200g of polyethylene glycol 600 is synthesized in the step S200, 0.24g of catalyst with the concentration of 0.02% is needed, 300g of polyethylene glycol 600 is added in the step S300, at this time, the content of the supported compound alkyl metal catalyst in the reaction kettle is only 0.06g, but 0.02% of catalyst with the concentration of 0.24g is needed for synthesizing 1200g of glycol block polyether 2400, and 0.18g of supported compound alkyl metal catalyst is needed to be added in a supplementary mode, so that the catalytic effect and the quality of the glycol block polyether are ensured.
The ethylene glycol block polyether has the advantages of low color, narrow molecular weight distribution and no need of post-treatment, so the production process is simple, the production cost is low, the supported compound alkyl metal catalyst is taken as a catalyst, the catalyst is an acid catalyst and has two active centers, compared with KOH, the catalyst has high catalytic activity and quick reaction time, the molecular weight distribution of the product is narrow, and the compound alkyl metal catalyst and a catalytic carrier (gamma-Al) 2 O 3 ) The combination firstly prevents the reaction intermediate from generating back biting reaction by the reaction in the pore canal of the carrier, thereby reducing the content of byproducts (cyclic polymer) in the product, secondly, the catalyst is a heterogeneous catalyst, and after the reaction is finished, the product can be filtered to recycle the catalyst, thereby further saving the cost.
In addition, the catalyst carrier is subjected to pretreatment of washing, filtering, drying and calcining in sequence before the supported compound alkyl metal catalyst is prepared, so that impurities and dehydration are removed, the acidity of the catalyst carrier is enhanced, more holes are formed, the interaction between the catalyst and the carrier is facilitated, and the activity of the supported catalyst is higher. In step S300, the ethylene glycol block polyether is obtained by filtration, and at the same time, the solid supported compound alkyl metal catalyst is filtered out, and the supported compound alkyl metal catalyst can be cleaned, dried and recycled.
The ethylene glycol block polyethers and the synthetic methods according to the present invention are further illustrated by the following specific examples and comparative examples, but the following examples should not be construed as limiting the scope of the claims.
[ example 1 ]
(1) Synthesis of polyethylene glycol 440: firstly, 100g of ethylene glycol and 0.14g of supported alkyl magnesium aluminum catalyst (Mg/Al=1:1) 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 120 ℃, 610g of ethylene oxide is dropwise added, the reaction temperature is controlled to 120-140 ℃, the reaction pressure is controlled to 0-0.2 MPa, the reaction kettle is cured for 0.5h, the temperature is reduced to 100 ℃ for degassing, and finally the temperature is reduced to 70 ℃ for discharging.
(2) Synthesis of ethylene glycol block polyether 1600: 220g of polyethylene glycol 440 and 0.16g of supported alkyl magnesium aluminum catalyst (Mg/Al=1:1) 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 115 ℃, 580g of propylene oxide is dropwise added, the reaction temperature is controlled to 115-118 ℃, the reaction pressure is controlled to 0-0.35 MPa, the reaction kettle is cured for 2.5h, the temperature is reduced to 100 ℃ for degassing, the temperature is reduced to 70 ℃, and finally sodium hydroxide is used for neutralization and discharging, thus obtaining the ethylene glycol block polyether.
[ example 2 ]
(1) Synthesis of polyethylene glycol 440: firstly, 100g of ethylene glycol and 0.22g of supported alkyl magnesium aluminum catalyst (Mg/Al=1:2) 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 120 ℃, 610g of ethylene oxide is dropwise added, the reaction temperature is controlled to 120-140 ℃, the reaction pressure is controlled to 0-0.2 MPa, the reaction kettle is cured for 0.5h, the temperature is reduced to 100 ℃ for degassing, and finally the temperature is reduced to 70 ℃ for discharging.
(2) Synthesis of ethylene glycol block polyether 2760: 220g of polyethylene glycol 440 and 0.42g of supported alkyl magnesium aluminum catalyst (Mg/Al=1:2) 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 115 ℃, 1160g of propylene oxide is dropwise added, the reaction temperature is controlled to 115-118 ℃, the reaction pressure is controlled to 0-0.35 MPa, the reaction kettle is cured for 2.5h, the temperature is reduced to 100 ℃ for degassing, the temperature is reduced to 70 ℃, and finally sodium hydroxide is used for neutralization and discharging, thus obtaining the ethylene glycol block polyether.
[ example 3 ]
(1) Synthesis of polyethylene glycol 440: firstly, 100g of ethylene glycol and 0.28g of supported alkyl magnesium aluminum catalyst (Mg/Al=1:3) 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 120 ℃, 610g of ethylene oxide is dropwise added, the reaction temperature is controlled to 120-140 ℃, the reaction pressure is controlled to 0-0.2 MPa, the reaction kettle is cured for 0.5h, the temperature is reduced to 100 ℃ for degassing, and finally the temperature is reduced to 70 ℃ for discharging.
(2) Synthesis of ethylene glycol Block polyether 3920: 220g of polyethylene glycol 440 and 0.80g of supported alkyl magnesium aluminum catalyst (Mg/Al=1:3) 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 115 ℃, 1740g of propylene oxide is dropwise added, the reaction temperature is controlled to 115-118 ℃, the reaction pressure is controlled to 0-0.35 MPa, the reaction kettle is cured for 2.5h, the temperature is reduced to 100 ℃ for degassing, the temperature is reduced to 70 ℃, and finally, the reaction kettle is neutralized by sodium hydroxide and is discharged, so that the ethylene glycol block polyether is obtained.
[ example 4 ]
(1) Synthesis of polyethylene glycol 880: firstly, 100g of ethylene glycol and 0.28g of supported alkyl magnesium aluminum catalyst (Mg/Al=1:4) 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 120 ℃, 1320g of ethylene oxide is dropwise added, the reaction temperature is controlled to 120-140 ℃, the reaction pressure is controlled to 0-0.2 MPa, the reaction kettle is cured for 0.5h, the temperature is reduced to 100 ℃ for degassing, and finally the temperature is reduced to 70 ℃ for discharging.
(2) Synthesis of ethylene glycol Block polyether 4360: 220g of polyethylene glycol 440 and 0.22g of supported alkyl magnesium aluminum catalyst (Mg/Al=1:4) 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 115 ℃, 870g of propylene oxide is dropwise added, the reaction temperature is controlled to 115-118 ℃, the reaction pressure is controlled to 0-0.35 MPa, the reaction kettle is cured for 2.5h, the temperature is reduced to 100 ℃ for degassing, the temperature is reduced to 70 ℃ at last, the neutralization with sodium hydroxide is carried out, and the ethylene glycol block polyether is obtained after discharging.
[ example 5 ]
(1) Synthesis of polyethylene glycol 1320: firstly, adding 62g of ethylene glycol and 0.40g of supported alkyl magnesium aluminum catalyst (Mg/Al=1:1) into a 2.5L high-pressure reaction kettle, sealing the reaction kettle, starting stirring and vacuumizing, then replacing gas in the kettle for 3 times by nitrogen, heating to 120 ℃, dropwise adding 1258g of ethylene oxide, controlling the reaction temperature to 120-140 ℃, controlling the reaction pressure to 0-0.2 MPa, curing for 0.5h, cooling to 100 ℃, degassing, and finally cooling to 70 ℃ for discharging.
(2) Synthesis of ethylene glycol Block polyether 3640: firstly, adding 440g of polyethylene glycol 440 and 0.37g of supported alkyl magnesium aluminum catalyst (Mg/Al=1:2) into a 2.5L high-pressure reaction kettle, sealing the reaction kettle, starting stirring and vacuumizing, then replacing gas in the kettle with nitrogen for 3 times, heating to 115 ℃, dropwise adding 774g of propylene oxide, controlling the reaction temperature to 115-118 ℃, controlling the reaction pressure to 0-0.35 MPa, curing for 2.5h, cooling to 100 ℃, degassing, finally cooling to 70 ℃, neutralizing with sodium hydroxide, and discharging to obtain the ethylene glycol block polyether.
[ example 6 ]
(1) Synthesis of polyethylene glycol 1760: firstly, adding 62g of ethylene glycol and 0.7g of supported alkyl magnesium aluminum catalyst (Mg/Al=1:2) into a 2.5L high-pressure reaction kettle, sealing the reaction kettle, starting stirring and vacuumizing, then replacing gas in the kettle for 3 times by nitrogen, heating to 120 ℃, dropwise adding 1698g of ethylene oxide, controlling the reaction temperature to 120-140 ℃, controlling the reaction pressure to 0-0.2 MPa, curing for 0.5h, cooling to 100 ℃, degassing, and finally cooling to 70 ℃ for discharging.
(2) Synthesis of ethylene glycol Block polyether 2920: firstly, adding 440g of polyethylene glycol 440 and 0.3g of supported alkyl magnesium aluminum catalyst (Mg/Al=1:4) into a 2.5L high-pressure reaction kettle, sealing the reaction kettle, starting stirring and vacuumizing, then replacing gas in the kettle with nitrogen for 3 times, heating to 115 ℃, dropwise adding 290g of propylene oxide, controlling the reaction temperature to 115-118 ℃, controlling the reaction pressure to 0-0.35 MPa, curing for 2.5h, cooling to 100 ℃, degassing, finally cooling to 70 ℃, neutralizing with sodium hydroxide, and discharging to obtain the ethylene glycol block polyether.
Examples 7 to 10
The operation of examples 7 to 10 was carried out in the same manner as in example 6, except that the supported metal alkyl catalyst used was a supported aluminum alkyl magnesium catalyst recovered from example 6, and the amount of the supported aluminum alkyl catalyst used in examples 7 to 10 was the same as in example 6 (a small amount of catalyst was lost after the catalyst treatment, and the catalyst was added).
Comparative examples 1 to 6
The specific implementation procedures of comparative examples 1 to 6 were the same as examples 1 to 6, respectively, except that the supported metal alkyl catalyst was replaced with potassium hydroxide, and the amount of potassium hydroxide was 10 times the amount of the supported metal alkyl catalyst used in the corresponding examples (since the activity of the potassium hydroxide catalyst was low, the reaction time required was too long if the amount was 0.01% to 0.04%), and neutralization was performed using glacial acetic acid.
[ comparative example 7 ]
Specific implementation of comparative example 7 the procedure was the same as in example 6, except that the supported, formulated metal alkyl catalyst was replaced with an aluminum alkyl magnesium catalyst.
Comparative example 8
Specific implementation of comparative example 8 the procedure was the same as in example 6, except that the supported metal alkyl catalyst was replaced with boron trifluoride etherate.
Table 1 is a table of process parameters for examples 1 to 6:
table 2 is a table of process parameters for comparative examples 1 to 6:
the color, weight average molecular weight, distribution coefficient and foam height of the ethylene glycol block polyethers obtained in examples 1 to 10 and comparative examples 1 to 8 were examined, and the examination results are shown in tables 3 to 5.
The adopted detection method comprises the following steps:
gel chromatography (GPC): tetrahydrofuran was used as the eluent, a differential refractive detector, and polyethylene glycol was used as the standard.
Foam performance test method: firstly, preparing 500ml of ultrapure water solution with the sample concentration of 0.2%, placing the ultrapure water solution into a 2000ml measuring cylinder, and keeping the temperature at 15 ℃ for 10 to 15 minutes; then a circulating pump is started, wherein the flow rate is 5L/min, the distance between a spray head and a measuring cylinder is 8cm, and the circulating pump is used for circularly brewing for 15 to 20 minutes; and finally, reading the foam height, stopping brewing, and recording the foam residual height after foam is defoamed to the bottom.
Table 3 shows the product index comparisons of examples 1 to 6 and comparative examples 1 to 6:
table 4 is the repetition of the supported alkyl magnesium aluminum catalyst:
table 5 shows the product index comparisons of example 6 with comparative examples 7 and 8:
as can be seen from Table 3, the ethylene glycol block polyether obtained by using the supported alkyl magnesium aluminum compound as the catalyst has lighter color, narrower distribution and better foam performance than the potassium hydroxide catalyst.
As can be seen from Table 4, the supported alkyl magnesium aluminum catalyst is reused for 5 times, the product indexes obtained by the supported alkyl magnesium aluminum catalyst meet the requirements, the catalyst can be reused, and the cost is saved.
As can be seen from Table 5, the supported alkyl magnesium aluminum complex is used as a catalyst, and the dioxane content and the byproducts are less than those of the alkyl magnesium aluminum complex and boron trifluoride diethyl ether solution; the supported metal alkyl catalyst can effectively prevent the generation of dioxane and overcomes the defect of more cationic polymerization byproducts.
According to the invention, through carrying out example experiments and comparative example experiments on the types and the contents of the catalyst, the EO/PO molar ratio, the molecular weight and the like, the invention finally discovers that the supported alkyl magnesium aluminum compound is used as the catalyst, the EO/PO molar ratio is 1:2-2:1, the molecular weight is 1600-4500, and the obtained ethylene glycol block polyether has the advantages of better emulsification, lubrication and low foam performance, fewer byproducts, narrow distribution, excellent product property, stable quality and wide application range.
FIG. 2 is a graph of the differential refractive signal of the ethylene glycol block polyether obtained in example 1, showing that the molecular weight distribution of the product of example 1 is better, and the result is the weight average molecular weight and distribution coefficient in Table 3; FIGS. 3 and 4 are respectively the 13C nuclear magnetic resonance spectra of the ethylene glycol block polyether obtained in example 1 13 C-NMR) and nuclear magnetic resonance hydrogen profile 1 H-NMR), it can be seen from FIGS. 3 and 4 that the molecular structure of the ethylene glycol block polyether of example 1 is composed of a polyoxyethylene ether chain and a polyoxypropylene ether chain.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, such changes and modifications are also intended to be within the scope of the invention.
Claims (5)
1. A method for synthesizing ethylene glycol block polyether is characterized in that the molecular structural general formula of the ethylene glycol block polyether is as follows:
wherein a and c are the number of epoxypropane in the molecule and b is the number of ethylene oxide in the molecule;
the ethylene glycol block polyether is prepared from polyethylene glycol and ethylene oxide, wherein the polyethylene glycol is prepared from a supported compound metal alkyl catalyst, ethylene glycol and ethylene oxide, the supported compound metal alkyl catalyst is prepared from a compound metal alkyl catalyst and a catalyst carrier, and the compound metal alkyl catalyst is prepared from MgEt 2 And AlEt 3 Is compounded to form the MgEt 2 And AlEt 3 The mass ratio of the catalyst carrier is 1:1-4, and the catalyst carrier is gamma-Al 2 O 3 ；
The synthesis method of the ethylene glycol block polyether is characterized by comprising the following steps of:
(1) Preparing a supported compound metal alkyl catalyst, namely compounding two metal alkyl catalysts into a compound metal alkyl catalyst, and then supporting the compound metal alkyl catalyst on a catalyst carrier to obtain the supported compound metal alkyl catalyst;
(2) Preparing polyethylene glycol, namely adding a supported compound alkyl metal catalyst into the polyethylene glycol serving as a raw material, adding ethylene oxide into the mixture to perform polymerization reaction to obtain polyethylene glycol, and performing vacuum degassing after the reaction is finished;
(3) Preparing ethylene glycol block polyether, namely adding a supported compound alkyl metal catalyst into polyethylene glycol serving as a raw material, adding propylene oxide into the mixture to perform polymerization reaction, and degassing and filtering the mixture after the reaction is finished to obtain the ethylene glycol block polyether.
2. The method for synthesizing according to claim 1, wherein the specific steps for preparing polyethylene glycol are: firstly adding ethylene glycol and a supported compound alkyl metal catalyst into a high-pressure reaction kettle, vacuumizing after sealing the reaction kettle, then purging with nitrogen, repeatedly placing nitrogen for a plurality of times, heating, adding ethylene oxide, curing until the pressure is almost unchanged under the internal pressure of the reaction kettle, and finally cooling, degassing and discharging; the times of repeated nitrogen placement are 3 times, then the temperature is raised to 120 ℃, after the ethylene oxide is added for 60min, the internal pressure of the reaction kettle is kept below 0.2MPa, and the temperature is reduced to 100 ℃ and then the degassing is carried out;
the specific steps for preparing the ethylene glycol block polyether are as follows: firstly adding polyethylene glycol into a reaction kettle, repeatedly placing nitrogen for a plurality of times, then heating, adding propylene oxide, curing until the pressure is almost unchanged under the internal pressure of the reaction kettle, and finally cooling, degassing and discharging; the times of repeatedly placing nitrogen are 3 times, then the temperature is raised to 115 ℃ and propylene oxide is added dropwise, after the propylene oxide is added dropwise at 3-4 h, the internal pressure of the reaction kettle is kept below 0.35MPa, and the temperature is lowered to 100 ℃ and then the degassing is carried out.
3. The method of synthesis according to claim 1, wherein the catalyst support is subjected to a pretreatment of washing, filtering, drying and calcining in sequence prior to the preparation of the supported complex metal alkyl catalyst.
4. The synthesis method according to claim 1, wherein in the step (2), the addition amount of the supported compound alkyl metal catalyst is 0.02% -0.04% of the total mass of polyethylene glycol.
5. The synthesis method according to claim 1, wherein in the step (3), the addition amount of the supported compound alkyl metal catalyst is 0.02% -0.04% of the total mass of the ethylene glycol block polyether.
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