Skeleton supported catalyst and method for preparing allyl alcohol polyoxyethylene ether by using the same

Abstract

To provide a skeleton supported catalyst and a method for producing allyl alcohol polyoxyethylene ether having a low by-product content by using the same.SOLUTION: A skeleton supported catalyst is a catalyst in which barium oxide, potassium oxide, and yttrium oxide are loaded within a copper skeleton, wherein the weight percentage occupied by the copper skeleton in the skeleton supported catalyst is 70-90%, and the molar ratio of the barium, potassium, and yttrium elements is 1:0.02-0.08:0.01-0.04. A method for producing allyl alcohol polyoxyethylene ether comprises putting the skeleton supported catalyst into a reaction vessel, incorporating nitrogen into the vessel, adding dried and dehydrated allyl alcohol or low molecular weight allyl alcohol polyoxyethylene ether into the reaction vessel, raising the temperature, and continuously introducing dried and dehydrated ethylene oxide for reaction; after the reaction is completed, lowering the temperature, filtering, and discharging the material to obtain the product.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to the technical field of the synthesis of organic polymer compounds, and specifically relates to a skeleton-supported catalyst and a method for producing aryl alcohol polyoxyethylene ether using the same.

Background Art

[0002] Aryl alcohol polyoxyethylene ether is an aryl alcohol derivative synthesized by the reaction of allyl alcohol with ethylene oxide (EO) under a catalytic action. Since there is a double bond in its structure, it can undergo a graft reaction with a hydrogen-containing silicone oil under the action of a platinum-based catalyst to obtain a polyether-modified silicone oil with high surface activity. Polyether-modified silicone oil is widely applied in many fields such as paint wetting agents and leveling agents, agricultural efficacy enhancers, printing and dyeing wetting agents, paper-making defoaming agents, water-reducing agents, etc., and has broad development prospects.

[0003] The high or low double bond retention rate and dihydroxy polyether by-product content of aryl alcohol polyoxyethylene ether are the keys to measuring the quality of aryl alcohol polyoxyethylene ether. High-quality polyether-modified silicone oil is based on aryl alcohol polyoxyethylene ether with a high double bond retention rate and a low content of dihydroxy polyether by-products. The double bond retention rate of aryl alcohol polyoxyethylene ether and the dihydroxy polyether content of by-products are the key factors affecting the performance and product quality of polyether-modified silicone oil. Currently, there are several reports on the synthesis method of aryl alcohol polyoxyethylene ether. For example, Guo Guolong et al. published "Research on the Manufacture and Application Performance of Aryl Alcohol Polyoxyethylene Ether by DMC Catalyst" in the journal "Daily Chemicals Science". This article synthesized aryl alcohol polyoxyethylene ether using a bimetallic cyanide complex catalyst (DMC) prepared by ZnCl2 and K3Co(CN)6 for the ethoxylation reaction catalyst, and the polyethylene glycol content of its by-products reached 1.78%. Patent CN201310222073.0 discloses a method for producing a polycarboxylic acid-based water-reducing agent macromonomer methyl allyl alcohol polyoxyethylene ether, which uses methyl allyl alcohol as an initiator, boron trifluoride-ethyl ether as a catalyst, undergoes an addition reaction with 5-10 mol of ethylene oxide, and further synthesizes a crude product with a higher molecular weight using an oxidizing agent, sodium hydroxide or sodium methanol as a catalyst, and then adds a neutralization reaction solution such as glacial acetic acid to obtain a finished product. This method has the following problems: 1. Using boron trifluoride-ethyl ether as a catalyst, boron trifluoride-ethyl ether is prone to self-polymerize ethylene oxide, generating dioxane and polyethylene glycol by-products, increasing the content of by-products and affecting the use performance of the product. 2. Directly neutralizing with acid without removing metal ions such as K and Na in the product, the obtained methacrylic alcohol polyoxyethylene ether cannot be applied to the synthesis of polyether-modified silicone oil because the K and Na metal ions in the system cause the deactivation of the chloroplatinic acid platinum-based catalyst.Patent CN201410157740.6 uses an intermediate product obtained by the reaction of methylallyl alcohol and lithium aluminum tetrahydride as a catalyst, methylallyl alcohol as an initiator, adds ethylene oxide and reacts to obtain a methylallyl alcohol oligomer, uses an alkali catalyst such as KOH, adds ethylene oxide and reacts to obtain a crude product of methylallyl alcohol polyoxyethylene ether, and adds glacial acetic acid for direct neutralization to obtain a finished product. This method also has the problem that various metal ions such as K, Na, aluminum, and lithium remain in the product, and the obtained methacryl alcohol polyoxyethylene ether cannot be applied to the synthesis of polyether-modified silicone oil. Moreover, due to the presence of various metal ions, when acid neutralization crystallization adsorption is adopted, the solubility of various metal salts is different, it is difficult to control crystallization, and there are incomplete problems. Patent CN202010754807.X invented a method for producing methacryl alcohol polyoxyethylene ether, which is a large monomer of a polycarboxylic acid water reducer. Using methacryl alcohol as an initiator and sodium hydride as a catalyst, a crude product of methacryl alcohol polyoxyethylene ether is synthesized, and glacial acetic acid is added for direct neutralization to produce a product. This process also has the problem that if acid neutralization is adopted without removing metal ions such as K and Na, the chloroplatinic acid platinum-based catalyst will be deactivated, and the finished product cannot be applied to polyether-modified silicone oil. Patent CN200910198310.8 discloses a method for producing allyl alcohol polyoxyethylene ether using allyl alcohol as a raw material, allyl alcohol sodium or allyl alcohol potassium as a catalyst, causing an addition reaction with ethylene oxide, adding glacial acetic acid for neutralization after the reaction is completed, and directly using a liquid with a precision of 35 - 75 μm for filtration with a filter bag after cooling to obtain a finished product of methacryloxyethylene ether. This method only involves simple neutralization and direct filtration, and a large amount of metal K and Na ions (>150 ppm) remain, the product cannot be applied to the synthesis of polyether-modified silicone oil, and it causes the problem of deactivation of the chloroplatinic acid platinum-based catalyst.

[0004] At present, the synthesis methods of aryl alcohol polyoxyethylene ethers provided by the prior art mainly have the following deficiencies. 1. Without considering the trace amounts of water carried by the raw materials ethylene oxide and allyl alcohol itself (commercially available ethylene oxide has about 0.02% water, and commercially available allyl alcohol has about 0.03% water), the water carried by these raw materials themselves is not removed, and allyl alcohol polyoxyethylene ether is directly synthesized. In the presence of a catalyst, water reacts with ethylene oxide to produce the by-product polyethylene glycol, and the by-product content is high (allyl alcohol polyoxyethylene ether molecular weight 500, polyethylene glycol content > 0.4%, allyl alcohol polyoxyethylene ether molecular weight 1000, polyethylene glycol content > 1.0%). On the other hand, the content of the active ingredient of the product is low, the molecular weight distribution is wide, which affects the performance of the product. 2. Ordinary catalysts such as KOH, sodium allyl alcoholate, and potassium allyl alcoholate are adopted, and metal ions such as K and Na are not removed during the post-treatment. Therefore, the obtained allyl alcohol polyoxyethylene ether cannot be applied to the synthesis of polyether-modified silicone oil.

[0005] Therefore, in order to solve the problems existing in the existing synthesis methods, such as high content of polyethylene glycol as a by-product, wide molecular weight distribution, and high metal ion content, it is necessary to develop a skeleton-supported catalyst and a manufacturing method of aryl alcohol polyoxyethylene ether using this catalyst. In addition, the aryl alcohol polyoxyethylene ether product can be used in the synthesis of polyether-modified silicone oil in fields such as high-end paints.

Summary of the Invention

[0006] In order to overcome the deficiencies of the prior art, one of the objectives of the present invention is to provide a skeleton-supported catalyst having a porous structure, a large specific surface area, high catalytic activity, good selectivity, a narrow molecular weight distribution of the product catalytically synthesized by this catalyst, and recyclability.

[0007] To solve the above problems, the technical means adopted by the present invention are as follows.

[0008] The skeleton-supported catalyst is a catalyst in which barium oxide, potassium oxide, and yttrium oxide are supported within a copper skeleton. Among them, the weight percentage of the copper skeleton in the skeleton-supported catalyst is 70-90%, and the molar ratio of the barium, potassium, and yttrium elements is 1:0.02-0.08:0.01-0.04.

[0009] The second object of the present invention is to provide a method for manufacturing a skeleton-supported catalyst, which includes step A: putting an aluminum-copper alloy into a potassium hydroxide solution for activation for 20-28 h, dissolving aluminum in the aluminum-copper alloy in the potassium hydroxide solution, filtering, washing with water to obtain a copper skeleton; step B: putting the copper skeleton into an aqueous barium hydroxide solution at 60-70 °C, slowly cooling to 35-45 °C while slowly stirring to supersaturate and precipitate barium hydroxide, filtering the copper skeleton particles with barium hydroxide precipitate attached, and calcining the copper skeleton particles at 700-800 °C for 2-4 h to obtain a copper skeleton supported with barium oxide; step C: using a mixed solution containing potassium hydroxide and yttrium nitrate to immerse or spray the copper skeleton supported with barium oxide for 2-5 min, filtering, calcining the copper skeleton at 400-500 °C for 2-4 h, and after cooling, internally supporting barium oxide, potassium oxide, and yttrium oxide on the copper skeleton.

[0010] In the above manufacturing method, the weight ratio of copper to aluminum in the aluminum-copper alloy in step A is 1:2-4, and the mass concentration of the potassium hydroxide solution is 25-35%.

[0011] As a preferred embodiment of the present invention, the particle sizes of the aluminum-copper alloy in step A and the copper skeleton particles in step B are both 200-1000 μm.

[0012] As a preferred embodiment of the present invention, the mass concentration of the aqueous barium hydroxide solution in step B is 15-20%.

[0013] As a preferred embodiment of the present invention, the mass concentration of potassium hydroxide in the mixed solution in step C is 20-30%, and the mass concentration of yttrium nitrate is 20-30%.

[0014] The third object of the present invention is to provide the application of the skeleton-supported catalyst as described above or the skeleton-supported catalyst produced by the above production method to the production of aryl alcohol polyoxyethylene ether.

[0015] The fourth object of the present invention is to provide a method for producing aryl alcohol polyoxyethylene ether using the above-mentioned skeleton-supported catalyst or the skeleton-supported catalyst produced by the above-mentioned production method. This method has simple steps and easy control. The aryl alcohol polyoxyethylene ether product produced by this method has a low by-product content, a high active ingredient content, a narrow molecular weight distribution, and excellent product performance.

[0016] The method for producing aryl alcohol polyoxyethylene ether using a skeleton-supported catalyst specifically includes:

[0017] S1: Put the skeleton-supported catalyst into a reaction kettle, after filling nitrogen into the kettle, add allyl alcohol or aryl alcohol polyoxyethylene ether with a molecular weight of 100-600 that has been dried to remove water into the reaction kettle, raise the temperature, and continue the reaction through ethylene oxide that has been dried to remove water;

[0018] S2: After the reaction is completed, lower the temperature, filter, discharge the raw materials, and produce the finished product of aryl alcohol polyoxyethylene ether.

[0019] As a preferred embodiment of the present invention, the dosage of the skeleton-supported catalyst in step S1 is 0.5-3.0% of the sum of the masses of allyl alcohol or aryl alcohol polyoxyethylene ether and ethylene oxide.

[0020] As a preferred embodiment of the present invention, the weight ratio of the allyl alcohol or aryl alcohol polyoxyethylene ether to ethylene oxide in step S1 is 1:0.75 to 68.

[0021] As a preferred embodiment of the present invention, in step S1, the reaction temperature for adding ethylene oxide is 90 to 140°C.

[0022] As a preferred embodiment of the present invention, in step S2, after cooling to 55 - 75°C, filtration is carried out to discharge the raw materials.

[0023] As a preferred embodiment of the present invention, the molecular weight of the finished product of the aryl alcohol polyoxyethylene ether is 100 - 4000, the polyethylene glycol content as a by - product in the finished product of the aryl alcohol polyoxyethylene ether is 0.3% or less, and the content of Na + and K + is 2 ppm or less.

[0024] The beneficial effects of the present invention are as follows compared with the prior art. 1. The skeleton - supported catalyst of the present invention has a porous structure, a large specific surface area, high catalytic activity, and good selectivity. When applied to the synthesis of aryl alcohol polyoxyethylene ether, it reacts with allyl alcohol without generating polyethylene glycol by - products containing bis - hydroxyl groups. Among them, barium oxide plays a main catalytic role with good catalytic selectivity. By supporting yttrium oxide and potassium oxide on the copper - skeleton catalyst supporting barium oxide, the reaction rate can be increased, and it can be guaranteed to obtain a product with a narrow molecular weight distribution. This is because the high reaction activity of potassium oxide and yttrium oxide exerts a synergistic effect, so that the synthesized aryl alcohol polyoxyethylene ether product has the advantage of a narrow molecular weight distribution. At the same time, this skeleton - supported catalyst is a solid catalyst, which is easy to separate and recycle. 2. The manufacturing method of the skeleton-supported catalyst provided by the present invention has low manufacturing costs, can be recycled, is environmentally friendly, is easy to operate, has high technical stability, and the catalyst manufactured by supporting various metal ions has high catalytic activity. 3. The present invention uses a skeleton-supported catalyst to catalyze the reaction of allyl alcohol and ethylene oxide. This catalyst does not react with allyl alcohol to produce polyethylene glycol by-products containing bis-hydroxyl groups, and well avoids the production of water by the reaction of ordinary catalysts such as KOH with allyl alcohol and further the production of polyethylene glycol, which is a by-product of the reaction of water with ethylene oxide, thereby reducing the effective ingredient of the product and affecting the product performance. At the same time, the metal ions in the skeleton-supported catalyst do not dissolve in the product, and the metal ion content in the product is reduced to 2 ppm or less, so the problem that the product cannot react with hydrogen-containing silicone oil without directly neutralizing with acid to remove metal ions by the conventional method is well avoided. The obtained aryl alcohol polyoxyethylene ether product can be applied to the system for synthesizing polyether-modified silicone oil by reacting with a trace amount of platinum-based catalyst and hydrogen-containing silicone oil, and the skeleton-supported catalyst is convenient for recovery. In addition, the present invention well removes water by drying both allyl alcohol and ethylene oxide, which are reaction raw materials, and avoids the production problem of polyethylene glycol, which is a by-product of the reaction of residual moisture in the reaction raw materials with ethylene oxide, and further reduces the by-product content in the product. 4. The aryl alcohol polyoxyethylene ether manufactured by the manufacturing method of the present invention has a significantly reduced by-product content, a high effective ingredient content, a narrow molecular weight distribution, a low metal ion content such as K and Na, excellent product performance, and can be applied to the synthesis of polyether-modified silicone oil in fields such as high-end paints.

Brief Description of the Drawings

[0025] Figure 1 is a physical comparison diagram of the finished polyether-modified silicone oil products manufactured using the aryl alcohol polyoxyethylene ethers manufactured in Example 1 and Comparative Example 1 of the present invention, respectively.

[0026] Figure 2 is a comparison diagram of actual products of polyether-modified silicone oil finished products manufactured using aryl alcohol polyoxyethylene ethers respectively manufactured using Example 2, Comparative Example 2, and Comparative Example 5 of the present invention.

[0027] Figure 3 is a comparison diagram of actual products of polyether-modified silicone oil finished products manufactured using aryl alcohol polyoxyethylene ethers respectively manufactured using Example 3, Comparative Example 3, and Comparative Example 6 of the present invention.

[0028] Figure 4 is a comparison diagram of actual products of polyether-modified silicone oil finished products manufactured using aryl alcohol polyoxyethylene ethers respectively manufactured in Example 4 and Comparative Example 4 of the present invention.

Embodiments for Carrying out the Invention

[0029] The method for manufacturing aryl alcohol polyoxyethylene ether using the skeleton-supported catalyst provided by the present invention includes the following steps.

[0030] S1. Put the skeleton-supported catalyst into the reaction kettle. After introducing nitrogen into the kettle, add allyl alcohol that has been dried to remove water to the reaction kettle. After heating the temperature to 90 - 140°C, continue to pass ethylene oxide that has been dried to remove water and carry out the reaction at 90 - 140°C. Among them, the dosage of the skeleton-supported catalyst is 0.5 - 3.0% of the sum of the masses of allyl alcohol and ethylene oxide, and the weight ratio of allyl alcohol to ethylene oxide is 1:0.75 - 68. The reaction equation of the above reaction is as follows JPEG2025112247000002.jpg19137

[0031] S2. After cooling the temperature to 55 - 75°C, filter to remove the raw materials and manufacture the finished product of aryl alcohol polyoxyethylene ether.

[0032] The molecular weight of the aryl alcohol polyoxyethylene ether produced by the above manufacturing method is 100 - 4000, the polyethylene glycol content, which is a by-product in the aryl alcohol polyoxyethylene ether, is 0.3% or less, and the Na + and K + content is 2 ppm or less.

[0033] In the above manufacturing method, the skeleton-supported catalyst is a catalyst in which barium oxide, potassium oxide, and yttrium oxide are supported within a copper skeleton. Among them, the weight percentage of the copper skeleton in the skeleton-supported catalyst is 70 - 90%, and the molar ratio of the barium, potassium, and yttrium elements is 1:0.02 - 0.08:0.01 - 0.04. The manufacturing method of this skeleton-supported catalyst is Step A: An aluminum-copper alloy with a particle size of 200 - 1000 μm and a weight ratio of copper to aluminum of 1:2 - 4 is placed in a potassium hydroxide solution with a mass concentration of 25 - 35% for activation. The aluminum in the aluminum-copper alloy is dissolved in the potassium hydroxide solution. After activation for 20 - 28 h, filtration and washing with water are carried out to obtain a copper skeleton. Step B: The copper skeleton is placed in an aqueous barium hydroxide solution with a mass concentration of 15 - 20% at 60 - 70 °C, and the temperature is slowly lowered to 35 - 45 °C while slowly stirring to supersaturate and precipitate barium hydroxide. After filtration, copper skeleton particles with barium hydroxide precipitates with a particle size of 200 - 1000 μm attached are selected, and the copper skeleton particles are calcined at 700 - 800 °C for 2 - 4 h to obtain a copper skeleton supporting barium oxide. Step C: Using a mixed solution containing potassium hydroxide with a mass concentration of 20 - 30% and yttrium nitrate with a mass concentration of 20 - 30%, the copper skeleton supporting barium oxide is immersed or sprayed for 2 - 5 min. Immediately after the time has passed, filtration is carried out, and then the copper skeleton is calcined at 400 - 500 °C for 2 - 4 h. After cooling, sealing, and packaging, a skeleton-supported catalyst supporting barium oxide, potassium oxide, and yttrium oxide is obtained.

[0034] Hereinafter, the present invention will be described in more detail based on specific embodiments.

[0035] Preparation of the reaction kettle before implementation: Wash, purge, and dry the pipeline for transporting reaction raw materials. Dry the reaction kettle until it is completely dry, cool it to room temperature, and reserve it for standby. The following examples illustrate the present invention but do not limit the protection scope of this patent. The molecular weight in the examples and comparative examples is Mn (number average molecular weight, measured by gel permeation chromatography GPC), the molecular weight distribution coefficient D (measured by gel permeation chromatography GPC), and the polyethylene glycol (PEG) content is measured by liquid chromatography. The surface tension in the application experiment is measured using the national standard GB / T5549-2010 method, and the wetting time (penetration power) is measured using the national standard GB / T11983-2008 method.

[0036] Manufacture of the skeleton-supported catalyst: Put 500 g of an aluminum-copper alloy with a particle size of 200 - 1000 μm and a weight ratio of copper to aluminum of 1:3 into 5 L of a potassium hydroxide solution with a mass concentration of 30% for activation. After 24 hours of activation, dissolve the aluminum in the alloy in the alkaline solution, filter and wash with water to obtain the copper skeleton. Put the copper skeleton into 3 L of an aqueous barium hydroxide solution with a mass concentration of 17% at 65 °C, and slowly cool it to 40 °C while slowly stirring to supersaturate barium hydroxide and slowly precipitate it. Filter and select copper skeleton particles with barium hydroxide precipitates of 200 - 1000 μm attached. Bake the copper skeleton particles at 700 - 800 °C for 3 hours to obtain a copper skeleton supported with barium oxide. Further, put this copper skeleton into a mixed solution containing potassium hydroxide with a mass concentration of 25% and yttrium nitrate with a mass concentration of 25%, immerse it for 3 minutes, filter the copper skeleton immediately when the time is up, bake the copper skeleton at 400 - 500 °C for 3 hours, then cool down, seal, and package to obtain a skeleton-supported catalyst supported with barium oxide, potassium oxide, and yttrium oxide. Example 1

[0037] The manufacturing method of aryl alcohol polyoxyethylene ether using the skeleton-supported catalyst includes the following steps.

[0038] S1. Charge 23.3 g of the skeletal-supported catalyst into the reaction kettle. After replacing the air in the kettle with N₂ three times, introduce 300 g of allyl alcohol that has been dried to remove water into the reaction kettle. After the addition of allyl alcohol is completed, heat up to 90 °C, and then continuously add 1255 g of ethylene oxide that has been dried to remove water to start the reaction. Control the reaction temperature at 90 - 140 °C. After the addition is completed, continue the reaction for 1 h.

[0039] S2. After the reaction is completed, extract the low-boiling substances using vacuum. Then cool down to 60 °C, filter, add the raw materials, and obtain the finished product of aryl alcohol polyoxyethylene ether. Example 2

[0040] The manufacturing method of aryl alcohol polyoxyethylene ether using a skeletal-supported catalyst includes the following steps.

[0041] S1. Charge 15.5 g of the skeletal-supported catalyst into the reaction kettle. After replacing the air in the kettle with N₂ three times, introduce 200 g of allyl alcohol that has been dried to remove water into the reaction kettle. After the addition of allyl alcohol is completed, heat up to 90 °C, and then continuously add 1350 g of ethylene oxide that has been dried to remove water to start the reaction. Control the reaction temperature at 90 - 140 °C. After the addition is completed, continue the reaction for 1 h.

[0042] S2. After the reaction is completed, extract the low-boiling substances using vacuum. Then cool down to 60 °C, filter, add the raw materials, and obtain the finished product of aryl alcohol polyoxyethylene ether. Example 3

[0043] The manufacturing method of aryl alcohol polyoxyethylene ether using a skeletal-supported catalyst includes the following steps.

[0044] S1. Charge 30.0 g of the skeletal-supported catalyst into the reaction kettle, replace the air in the kettle three times with N2, then introduce 300 g of the dried and water-removed aryl alcohol polyoxyethylene ether produced in Example 1 into the reaction kettle. After the introduction of the aryl alcohol polyoxyethylene ether is completed, heat up to 90 °C, and continuously add 1250 g of the dried and water-removed ethylene oxide to start the reaction. Control the reaction temperature at 90 - 140 °C, complete the addition, and continue the reaction for 1 h.

[0045] S2. After the reaction is completed, extract the low-boiling substances using vacuum, then cool down to 60 °C, filter, add the raw materials, and obtain the finished product of aryl alcohol polyoxyethylene ether. Example 4

[0046] The manufacturing method of aryl alcohol polyoxyethylene ether using a skeletal-supported catalyst includes the following steps.

[0047] S1. Charge 38.0 g of the skeletal-supported catalyst into the reaction kettle, replace the air in the kettle three times with N2, then introduce 200 g of the dried and water-removed aryl alcohol polyoxyethylene ether produced in Example 1 into the reaction kettle. After the introduction of the aryl alcohol polyoxyethylene ether is completed, heat up to 90 °C, and continuously add 1350 g of the dried and water-removed ethylene oxide to start the reaction. Control the reaction temperature at 90 - 140 °C, complete the addition, and continue the reaction for 1 h.

[0048] S2. After the reaction is completed, extract the low-boiling substances using vacuum, then cool down to 60 °C, filter, add the raw materials, and obtain the finished product of aryl alcohol polyoxyethylene ether. Comparative Example 1

[0049] Take the manufacturing process disclosed in Chinese Patent CN202010754807.X as Comparative Example 1. The specific steps are as follows.

[0050] 300 g of allyl alcohol that has not been dried to remove water was directly charged into a reaction kettle filled with N2 that had replaced the allyl alcohol. After the addition of allyl alcohol was completed, 0.75 g of sodium hydride was added and reacted. After the reaction was completed, the hydrogen gas generated by the reaction of allyl alcohol and metallic sodium was evacuated under vacuum. The temperature was raised to 90 °C, and 1255 g of ethylene oxide that had not been dried to remove water was continuously added to initiate the reaction. The reaction temperature was controlled at 90 - 110 °C. After the addition was completed, the reaction was continued for 2 hours. After the reaction was completed and the low-boiling substances were extracted using vacuum, the temperature was lowered to 70 °C, and a crude product of aryl alcohol polyoxyethylene ether was produced. After discharging 500 g of the crude product, 1.3 g of glacial acetic acid and the produced aryl alcohol polyoxyethylene ether were added. Comparative Example 2

[0051] The difference between this comparative example and Comparative Example 1 is that the dosage of allyl alcohol is 200 g, the dosage of sodium hydride is 0.6 g, the dosage of ethylene oxide is 1350 g, and the dosage of glacial acetic acid is 1.5 g, and other process conditions are the same as those in Comparative Example 1. Comparative Example 3

[0052] The difference between this comparative example and Comparative Example 1 is that the reaction raw material is the crude product of aryl alcohol polyoxyethylene ether produced in Comparative Example 1, its dosage is 300 g, the dosage of sodium hydride is 0.5 g, the dosage of ethylene oxide is 1250 g, and the dosage of glacial acetic acid is 1.6 g, and other process conditions are the same as those in Comparative Example 1. Comparative Example 4

[0053] The difference between this comparative example and Comparative Example 1 is that the reaction raw material is the crude product of aryl alcohol polyoxyethylene ether produced in Comparative Example 1, its dosage is 200 g, the dosage of sodium hydride is 1.0 g, the dosage of ethylene oxide is 1350 g, and the dosage of glacial acetic acid is 2.7 g, and other process conditions are the same as those in Comparative Example 1. Comparative Example 5

[0054] The manufacturing method disclosed in Chinese Patent CN200910198310.8 was used as Comparative Example 5, and the specific steps are as follows.

[0055] First, replace the air in the reactor with nitrogen, add 196.7 g of allyl alcohol that has not been dried to remove water, and add 2.0 g of sodium allyl alcohol catalyst. Replace the air in the reactor with nitrogen, start stirring, heat up to the set reaction temperature, add 500 g of ethylene oxide that has not been dried to remove water and react. The reaction temperature is 90 - 110°C. Complete the reaction, cool down to 60°C, and remove unreacted ethylene oxide and low molecular weight substances by vacuum extraction. Maintain the system pressure at -0.1 to -0.05 MPa and maintain the time for 30 min.

[0056] Start stirring, and at the same time, add 2.65 g of sodium allyl alcohol catalyst to the reactor and replace the gas in the kettle with N2. Heat up to the set reaction temperature, react through 854 g of ethylene oxide, and control the reaction pressure at 0 - 0.4 MPa. After the reaction is completed, add 3.5 g of acetic acid to neutralize the product, cool it, and then filter the product using a liquid filtration bag with a precision of 50 μm to obtain an allyl polyoxyethylene ether product. Comparative Example 6

[0057] Take the production method disclosed in Chinese Patent CN200910198310.8 as Comparative Example 6, and the specific steps are as follows.

[0058] First, replace the air in the reactor with nitrogen, add 296.6 g of allyl alcohol that has not been dried to remove water, and add 4.7 g of sodium allyl alcohol catalyst. Replace the air in the reactor with nitrogen, start stirring, heat up to the set reaction temperature, add 1250 g of ethylene oxide that has not been dried to remove water and react. The reaction temperature is 90 - 110°C. Complete the reaction, cool down to 60°C, and discharge 1301 g of the material.

[0059] Start stirring, and at the same time, add 1.5 g of allyl alcohol sodium catalyst to the reactor, and replace the gas in the kettle with N2. Heat up to the set reaction temperature, react through 1050 g of ethylene oxide, and control the reaction pressure at 0 - 0.4 MPa. After the reaction is completed, add 1.7 g of acetic acid to neutralize the product, cool it, and then filter the product using a liquid filtration bag with an accuracy of 50 μm to obtain an allyl polyoxyethylene ether product.

[0060] I. Performance comparison test of allyl polyoxyethylene ether

[0061] For the finished allyl polyoxyethylene ethers produced in Examples 1 - 4 and Comparative Examples 1 - 6, measurements were respectively carried out on the content of polyethylene glycol as a by - product, the content of Na+ and K+, the number - average molecular weight and the molecular weight distribution, and the results are shown in Table 1.

[0062] Table 1: Performance comparison of allyl polyoxyethylene ethers in Examples 1 - 4 and Comparative Examples 1 - 6 JPEG2025112247000003.jpg39164

[0063] As can be seen from the data in Table 1, when the usage amounts of the raw materials allyl alcohol and ethylene oxide are the same, the aryl alcohol polyoxyethylene ethers synthesized in Examples 1 - 4 using the production method of the present invention have a higher molecular weight (3 - 10% higher) than those in Comparative Examples 1 - 4, the molecular weight distribution is significantly narrower, and the content of polyethylene glycol, which is a by - product in Comparative Examples 1 - 4, is more than 10 times higher than that of the products in Examples 1 - 4. As can be seen from the comparison between Examples 2 - 3 and Comparative Examples 5 - 6, when the usage ratios of the raw materials allyl alcohol and ethylene oxide are the same (the molecular weight design is the same), the aryl alcohol polyoxyethylene ethers synthesized in Examples 2 - 3 using the method of the present invention have a higher molecular weight (5 - 7% higher) than those in Comparative Examples 5 - 6, the molecular weight distribution is significantly narrower, but the content of polyethylene glycol in Comparative Examples 5 - 6 is more than 10 times higher than that of the products in Examples 2 - 3. Therefore, it is explained that the quality of the products synthesized by the method of the present invention is significantly improved compared with the conventional synthesis methods.

[0064] II. Application Performance Test of Allyl Polyoxyethylene Ether

[0065] The finished products of allyl polyoxyethylene ether produced in Examples 1-4 and Comparative Examples 1-6 were applied to the synthesis of polyether-modified silicone oil, and the specific synthesis method is as follows.

[0066] The reaction raw materials are the finished products of allyl polyoxyethylene ether produced in Examples 1-4 and Comparative Examples 1-6, hydrogen-containing silicone oil with a hydrogen content of 0.16%, and a mass concentration of 1% platinum chloride acid ethanol solution.

[0067] Synthesis process: The measured aryl alcohol polyoxyethylene ether and hydrogen-containing silicone oil were put into a reaction kettle, the air in the kettle was replaced with N2, the temperature was raised while stirring, and after the temperature rose to 90 °C, it was kept warm stably at 90 °C for 5 min. The holding time was maintained until the catalyst platinum chloride acid was added. At the same time, heating was stopped, the highest temperature during the reaction and the reaction process was recorded and observed. After reacting for 30 min, the raw materials were put in. The appearance of the finished product of polyether-modified silicone oil was observed, and the surface tension and penetration power of the finished product of polyether-modified silicone oil were measured, and the results are shown in Table 2 and Figures 1-4.

[0068] Table 2: Performance Comparison Results of Finished Products of Polyether-Modified Silicone Oil JPEG2025112247000004.jpg172164

[0069] As can be seen from Table 2 and FIGS. 1 to 4, using aryl alcohol polyoxyethylene ethers with the same raw material ratio and the same designed molecular weight, and using the same amount of chloroplatinic acid catalyst and hydrogen-containing silicone oil, polyether-modified silicone oils were synthesized. The polyether-modified silicone oil products synthesized using the aryl alcohol polyoxyethylene ethers produced in Examples 1 to 4 are all transparent liquids. However, the polyether-modified silicone oil products synthesized using the aryl alcohol polyoxyethylene ethers produced in Comparative Examples 1 to 6 are all milky white and layered. It is explained that the aryl alcohol polyoxyethylene ether produced in the present invention completely reacts with the hydrogen-containing silicone oil to form a transparent liquid. However, the reactions in Comparative Examples 1 to 6 are not complete, resulting in a layered and milky white heterogeneous solution. As can also be seen from the maximum temperature during the reaction process, the maximum temperature during the reaction process of the aryl alcohol polyoxyethylene ether of the present invention is 115°C or higher, which explains that the overall material temperature rises due to the generation of a large amount of reaction heat. However, the maximum temperature during the reaction process of the aryl alcohol polyoxyethylene ether in Comparative Examples 1 to 6 is 90°C at the start, the reaction heat is not obvious, and basically no reaction occurs, so the temperature does not rise. The surface tension of the polyether-modified silicone oils produced in Examples 1 to 4 was significantly lower than that in Comparative Examples 1 to 6, and it was explained that its surface activity was significantly improved compared to Comparative Examples 1 to 6 (the lower the surface tension, the stronger the surface activity). In terms of wetting time, the polyether-modified silicone oils synthesized using the aryl alcohol polyoxyethylene ethers obtained in Examples 1 to 4 were similarly significantly shorter than the polyether-modified silicone oils synthesized using the aryl alcohol polyoxyethylene ethers produced in Comparative Examples 1 to 6. The polyether-modified silicone oils synthesized in Comparative Examples 1 to 6 all exceeded 5 minutes and had relatively obvious wetting power. The wetting time of the polyether-modified silicone oils synthesized using the aryl alcohol polyoxyethylene ethers produced in Examples 1 to 4 was 30 seconds or less.As described above, the aryl alcohol polyoxyethylene ether produced by the production method of the present invention can be suitably applied to the synthesis of polyether-modified silicone oil in fields such as high-end paints.

[0070] The above embodiments are merely preferred embodiments of the present invention, and thus cannot limit the protection scope of the present invention. Any non-substantial changes and substitutions made by those skilled in the art based on the present invention belong to the protection scope required by the present invention.

Claims

1. A skeleton-supported catalyst, wherein barium oxide, potassium oxide, and yttrium oxide are supported within a copper skeleton, wherein, among them, the weight percentage of the copper skeleton in the skeleton-supported catalyst is 70 to 90%, and the molar ratio of the barium, potassium, and yttrium elements is 1:0.02 to 0.08:0.01 to 0.

04. A skeleton-supported catalyst characterized by this.

2. The fact that the barium oxide, potassium oxide, and yttrium oxide are supported within the copper skeleton comprises: Step A: putting an aluminum-copper alloy into a potassium hydroxide solution and activating it for 20 to 28 h, dissolving aluminum in the aluminum-copper alloy in the potassium hydroxide solution, filtering, and washing with water to obtain a copper skeleton; Step B: putting the copper skeleton into an aqueous barium hydroxide solution at 60 to 70 °C, slowly cooling it to 35 to 45 °C while slowly stirring, supersaturating and precipitating barium hydroxide, filtering the copper skeleton particles with barium hydroxide precipitate attached, and calcining the copper skeleton particles at 700 to 800 °C for 2 to 4 h to obtain a copper skeleton supporting barium oxide; Step C: using a mixed solution containing potassium hydroxide and yttrium nitrate to immerse or spray the copper skeleton supporting barium oxide for 2 to 5 min, filtering, calcining the copper skeleton at 400 to 500 °C for 2 to 4 h, and after cooling, supporting barium oxide, potassium oxide, and yttrium oxide within the copper skeleton. A skeleton-supported catalyst according to Claim 1, characterized by this.

3. In the aluminum-copper alloy in Step A, the weight ratio of copper to aluminum is 1:2 to 4, and the mass concentration of the potassium hydroxide solution is 25 to 35%. A skeleton-supported catalyst according to Claim 2, characterized by this.

4. The particle sizes of the aluminum-copper alloy in Step A and the copper skeleton particles in Step B are both 200 to 1000 μm. A skeleton-supported catalyst according to Claim 2, characterized by this.

5. The mass concentration of the aqueous barium hydroxide solution in Step B is 15 to 20%. A skeleton-supported catalyst according to Claim 2, characterized by this.

6. In the mixed solution in Step C, the mass concentration of potassium hydroxide is 20 to 30%, and the mass concentration of yttrium nitrate is 20 to 30%. A skeleton-supported catalyst according to Claim 2, characterized by this.

7. The method for producing an aryl alcohol polyoxyethylene ether using the skeletal supported catalyst according to claim 1 is as follows: S1: Put the skeletal supported catalyst into a reaction kettle, introduce nitrogen into the kettle, then add allyl alcohol that has been dried to remove water or an aryl alcohol polyoxyethylene ether with a molecular weight of 100 - 600 into the reaction kettle, raise the temperature, and continue the reaction by passing ethylene oxide that has been dried to remove water. S2: After the reaction is completed, lower the temperature, filter, discharge the raw materials, and produce the finished product of the aryl alcohol polyoxyethylene ether. The method for producing an aryl alcohol polyoxyethylene ether is characterized by the above steps.

8. The dosage of the skeletal supported catalyst in step S1 is 0.5 - 3.0% of the sum of the masses of allyl alcohol or aryl alcohol polyoxyethylene ether and ethylene oxide, and / or The weight ratio of the allyl alcohol or aryl alcohol polyoxyethylene ether to ethylene oxide in step S1 is 1:0.75 - 68, and / or In step S1, after raising the temperature to 90 - 140 °C, start to continue by passing ethylene oxide, and / or In step S1, the reaction temperature for adding ethylene oxide is 90 - 140 °C. The method for producing an aryl alcohol polyoxyethylene ether according to claim 7 is characterized by the above steps.

9. In step S2, after lowering the temperature to 55 - 75 °C, filter and discharge the raw materials. The method for producing an aryl alcohol polyoxyethylene ether according to claim 7 is characterized by the above steps.

10. The molecular weight of the finished product of the aryl alcohol polyoxyethylene ether is 100 - 4000, the polyethylene glycol content, which is a by-product in the finished product of the aryl alcohol polyoxyethylene ether, is 0.3% or less, and the Na ＋ and K ＋ content is 2 ppm or less. The method for producing an aryl alcohol polyoxyethylene ether according to claim 7, characterized by this.

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