Supported skeleton catalyst and method for producing aryl alcohol polyoxyethylene ether 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 organic polymer compound synthesis, 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 allyl alcohol derivative synthesized by the reaction of allyl alcohol with ethylene oxide (EO) under catalytic action. Due to the presence of a double bond in its structure, it can undergo a graft reaction with hydrogen-containing silicone oil under the action of a platinum-based catalyst, thereby obtaining polyether-modified silicone oil with high surface activity. Polyether-modified silicone oil is widely applied in many fields such as coating wetting agents, leveling agents, pesticide efficacy enhancers, textile printing wetting agents, papermaking defoamers, and water reducing agents, and has broad development prospects.

[0003] The double bond retention rate and dihydroxypolyether byproduct content of aryl alcohol polyoxyethylene ether are key indicators of 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 low dihydroxypolyether byproduct content. The double bond retention rate of aryl alcohol polyoxyethylene ether and the dihydroxypolyether byproduct content are binding factors that affect the performance and product quality of polyether-modified silicone oil. Currently, there are several reports on methods for synthesizing aryl alcohol polyoxyethylene ether. For example, Guo Guolong et al. published "Study on the Production of Aryl Alcohol Polyoxyethylene Ether by DMC Catalyst and its Application Performance" in the journal "Daily Chemical Science." This paper describes the synthesis of aryl alcohol polyoxyethylene ether using a bimetallic cyano complex catalyst (DMC) produced from ZnCl2 and K3Co(CN)6 as a catalyst for the ethoxylation reaction, with a polyethylene glycol byproduct content reaching 1.78%. Patent CN201310222073.0 discloses a method for producing polycarboxylic acid-based water-reducing agent large monomer methyl allyl alcohol polyoxyethylene ether, in which methyl allyl alcohol is used as an initiator, boron trifluoride-ethyl ether is used as a catalyst, an addition reaction occurs with 5-10 mol of ethylene oxide, and a crude product with a higher molecular weight is synthesized using a hydroxide agent, sodium hydroxide, or sodium methanol as a catalyst, and then a neutralization reaction solution such as glacial acetic acid is added to obtain the finished product. This method has the following problems: 1. Boron trifluoride-ethyl ether is used as a catalyst, and boron trifluoride-ethyl ether readily self-polymerizes ethylene oxide, producing dioxane and polyethylene glycol by-products, increasing the by-product content and affecting the usability of the product. 2. Direct neutralization using acid without removing metal ions such as K and Na from the product results in methacrylic alcohol polyoxyethylene ether that cannot be used for the synthesis of polyether-modified silicone oil. This is because the K and Na metal ions in the system cause deactivation of the platinum chlorplatinate catalyst.Patent CN201410157740.6 uses an intermediate product obtained by the reaction of methyl allyl alcohol and lithium tetrahydroaluminum as a catalyst. Methyl allyl alcohol is used as an initiator, and ethylene oxide is added to react to obtain a methyl allyl alcohol oligomer. Using an alkaline catalyst such as KOH, ethylene oxide is added to react to obtain a crude methyl allyl alcohol polyoxyethylene ether, and the finished product is obtained by direct neutralization with glacial acetic acid. However, this method has the problem of various metal ions such as K, Na, aluminum, and lithium remaining in the product. The obtained methacrylic alcohol polyoxyethylene ether cannot be used in the synthesis of polyether-modified silicone oil. Furthermore, because various metal ions are present, if acid neutralization crystal adsorption is employed, the solubility of each type of metal salt differs, making crystal control difficult and resulting in an incomplete process. Patent CN202010754807.X invents a method for producing methacrylic alcohol polyoxyethylene ether, a major monomer of polycarboxylic acid water-reducing agents. It synthesizes crude methacrylic alcohol polyoxyethylene ether using methacrylic alcohol as an initiator and sodium hydride as a catalyst, and then directly neutralizes it with glacial acetic acid to produce the product. This process also has the problem that if acid neutralization is used without removing metal ions such as K and Na, the platinum chlorplatinate catalyst becomes inactive, 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 and sodium allyl alcohol or potassium allyl alcohol as a catalyst, undergoing an addition reaction with ethylene oxide, neutralizing with glacial acetic acid after the reaction is complete, and after cooling, filtering the finished product of methacrylic alcohol polyoxyethylene ether using a filtration bag with a liquid thickness of 35-75 μm directly. This method involves only simple neutralization and direct filtration, which leaves behind large amounts of metallic K and Na ions (>150 ppm). This has the problem of preventing the product from being used in the synthesis of polyether-modified silicone oil and causing inactivation of platinum chlorplatinate catalysts.

[0004] Currently, conventional methods for synthesizing aryl alcohol polyoxyethylene ethers have the following main shortcomings: 1. They do not take into account the trace amounts of water contained in the raw materials, ethylene oxide and allyl alcohol (commercial ethylene oxide contains approximately 0.02% water, and commercial allyl alcohol contains approximately 0.03% water). Without removing the water contained in these raw materials, allyl alcohol polyoxyethylene ether is synthesized as is, and in the presence of a catalyst, the water reacts with the ethylene oxide to produce the by-product polyethylene glycol. 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%), while the content of the active ingredient in the product is low, the molecular weight distribution is wide, and it affects the performance of the product. 2. Conventional catalysts such as KOH, sodium allyl alcohol, and potassium allyl alcohol are used, and metal ions such as K and Na are not removed during post-treatment. As a result, the obtained allyl alcohol polyoxyethylene ether could not be used for the synthesis of polyether-modified silicone oil.

[0005] To achieve this, it is necessary to develop a skeletal-supported catalyst and a method for producing aryl alcohol polyoxyethylene ether using it, in order to solve the problems of existing synthesis methods, which have a high polyethylene glycol content, a broad molecular weight distribution, and a high metal ion content as by-products. Furthermore, the aryl alcohol polyoxyethylene ether product can be used in the synthesis of polyether-modified silicone oils for fields such as high-end paints. [Overview of the project]

[0006] To overcome the shortcomings of conventional technology, one of the objectives of the present invention is to provide a skeletal-supported catalyst that has a porous structure, a large specific surface area, high catalytic activity, good selectivity, a narrow molecular weight distribution of the product synthesized with this catalyst, and is recyclable.

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

[0008] The skeletal-supported catalyst is a catalyst in which barium oxide, potassium oxide, and yttrium oxide are supported within a copper framework, with the copper framework accounting for 70-90% of the total weight of the skeletal-supported catalyst, and the ratio of the amounts of barium, potassium, and yttrium is 1:0.02-0.08:0.01-0.04.

[0009] The two objectives of the present invention are: Step A: Activate an aluminum-copper alloy in a potassium hydroxide solution for 20-28 hours to dissolve the aluminum in the aluminum-copper alloy in the potassium hydroxide solution, filter, wash with water to obtain a copper frame; and Step B: Place the copper frame in a barium hydroxide aqueous solution at 60-70°C, slowly cool to 35-45°C while slowly stirring to allow barium hydroxide to supersaturate and precipitate, filter the copper frame particles to which the barium hydroxide precipitate has adhered. The present invention provides a method for producing a frame-supported catalyst, comprising: step C: calcining copper frame particles at 700-800°C for 2-4 hours to obtain a copper frame supporting barium oxide; and step C: immersing or spraying the barium oxide-supported copper frame with a mixed solution containing potassium hydroxide and yttrium nitrate for 2-5 minutes, filtering, calcining the copper frame at 400-500°C for 2-4 hours, and after cooling, internally supporting barium oxide, potassium oxide, and yttrium oxide on the copper frame.

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

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

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

[0013] In 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] A third objective of the present invention is to provide the application of the above-described skeleton-supported catalyst or the skeleton-supported catalyst produced by the above-described manufacturing method to the production of aryl alcohol polyoxyethylene ethers.

[0015] The fourth object of the present invention is to provide a method for producing aryl alcohol polyoxyethylene ether using the above-described skeleton-supported catalyst or a skeleton-supported catalyst produced by the above-described production method, the method being simple and easy to control, and the aryl alcohol polyoxyethylene ether product produced by this method having 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 skeletal-supported catalyst is, specifically,

[0017] S1: The skeletal-supported catalyst is placed in a reaction vessel, nitrogen is introduced into the vessel, then allyl alcohol or aryl alcohol polyoxyethylene ether with a molecular weight of 100-600 is added to the reaction vessel, the temperature is raised, and the reaction is continued by passing dried ethylene oxide through it.

[0018] S2: After the reaction is complete, the temperature is lowered, the mixture is filtered, the raw materials are removed, and the finished aryl alcohol polyoxyethylene ether is produced.

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

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

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

[0022] In a preferred embodiment of the present invention, in step S2, the temperature is lowered to 55-75°C, then filtered, and the raw material is removed.

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

[0024] The beneficial effects of the present invention compared to the prior art are as follows: 1. The skeletal-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 ethers, it does not react with allyl alcohol to produce polyethylene glycol byproducts containing bishydroxyl groups. In this process, barium oxide plays the main catalytic role and exhibits good catalytic selectivity. By supporting yttrium oxide and potassium oxide on a copper skeletal catalyst supported with barium oxide, the reaction rate can be accelerated, and it is guaranteed that a product with a narrow molecular weight distribution can be obtained. This is because the high reactive activity of potassium oxide and yttrium oxide exerts a synergistic effect, resulting in the synthesized aryl alcohol polyoxyethylene ether product having the advantage of a narrow molecular weight distribution. At the same time, this skeletal-supported catalyst is a solid catalyst, making separation and recycling easy. 2. The method for producing a framework-supported catalyst provided by the present invention has low production cost, can be recycled and regenerated, is environmentally friendly, simple in operation, high in technical stability, and the catalyst produced by supporting a variety of metal ions has high catalytic activity. 3. The present invention uses a framework-supported catalyst to catalyze the reaction of allyl alcohol and ethylene oxide. The catalyst does not react with allyl alcohol to produce a polyethylene glycol by-product containing a bishydroxyl group, and effectively avoids the generation of water caused by the reaction of conventional catalysts such as KOH with allyl alcohol, and further the generation of polyethylene glycol which is a by-product from the reaction of water with ethylene oxide, which would otherwise reduce the content of active ingredients in the product and affect product performance. At the same time, the metal ions in the framework-supported catalyst do not dissolve in the product, and the content of metal ions in the product is controlled to be 2ppm or less, which effectively avoids the problem that in conventional methods, direct neutralization with acid cannot avoid the inability to react the product with hydrogen-containing silicone oil without removing metal ions. The obtained allyl alcohol polyoxyethylene ether product can be applied to a system for synthesizing polyether-modified silicone oil by reacting a trace amount of platinum-based catalyst with hydrogen-containing silicone oil, and the framework-supported catalyst is convenient for recovery. In addition, the present invention carries out drying removal of water from both the reaction raw materials allyl alcohol and ethylene oxide, which effectively avoids the problem of producing polyethylene glycol, a by-product resulting from the reaction of residual moisture in the reaction raw materials with ethylene oxide, and further reduces the content of by-products in the product. 4. The allyl alcohol polyoxyethylene ether produced by the production method of the present invention has a significantly reduced content of by-products, high content of active ingredients, narrow molecular weight distribution, low content of metal ions such as K and Na, and excellent product performance, which enables it to be applied to the synthesis of polyether-modified silicone oil in fields such as high-end coatings. [BRIEF DESCRIPTION OF THE DRAWINGS]

[0025] Figure 1 is a physical comparison diagram of finished polyether-modified silicone oil products respectively prepared by using the allyl alcohol polyoxyethylene ether produced in Example 1 of the present invention and Comparative Example 1.

[0026] Fig. 2 is a physical comparison diagram of finished polyether-modified silicone oils respectively produced by using aryl alcohol polyoxyethylene ether prepared in Example 2 of the present invention, Comparative Example 2 and Comparative Example 5.

[0027] Fig. 3 is a physical comparison diagram of finished polyether-modified silicone oils respectively produced by using aryl alcohol polyoxyethylene ether prepared in Example 3 of the present invention, Comparative Example 3 and Comparative Example 6.

[0028] Fig. 4 is a physical comparison diagram of finished polyether-modified silicone oils respectively produced by using aryl alcohol polyoxyethylene ether prepared in Example 4 of the present invention and Comparative Example 4. DESCRIPTION OF EMBODIMENTS

[0029] The method for producing aryl alcohol polyoxyethylene ether using a framework-supported catalyst provided by the present invention comprises the following steps:

[0030] S1: adding a framework-supported catalyst into a reaction kettle, replacing the interior of the kettle with nitrogen, then adding dried and dehydrated allyl alcohol into the reaction kettle, raising the temperature to 90 to 140°C, then introducing dried and dehydrated ethylene oxide to continue the reaction at 90 to 140°C, wherein the dosage of the framework-supported catalyst is 0.5 to 3.0% of the total mass of allyl alcohol and ethylene oxide, the weight ratio of allyl alcohol to ethylene oxide is 1:0.75 to 68, and the reaction equation of the above reaction is as follows JPEG0007912273000001.jpg19137

[0031] S2: lowering the temperature to 55 to 75°C, then performing filtration, discharging the material, to obtain a finished aryl alcohol polyoxyethylene ether product.

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

[0033] In the above manufacturing method, the skeletal-supported catalyst is a catalyst in which barium oxide, potassium oxide, and yttrium oxide are supported within a copper frame, with the copper frame accounting for 70-90% of the weight of the skeletal-supported catalyst, and the ratio of the amounts of barium, potassium, and yttrium elements being 1:0.02-0.08:0.01-0.04. The manufacturing method for this skeletal-supported catalyst is as follows: Step A involves activating an aluminum-copper alloy with a particle size of 200-1000 μm and a copper-to-aluminum weight ratio of 1:2-4 in a 25-35% potassium hydroxide solution to dissolve the aluminum in the alloy. After activating for 20-28 hours, the alloy is filtered and washed with water to obtain a copper frame. Step B involves placing the copper framework into a 15-20% mass concentration barium hydroxide aqueous solution at 60-70°C, slowly cooling it to 35-45°C while slowly stirring to allow barium hydroxide to supersaturate and precipitate. The solution is then filtered to select copper framework particles with barium hydroxide precipitates of 200-1000 μm attached, and these particles are calcined at 700-800°C for 2-4 hours to obtain copper frameworks supported with barium oxide. Step C involves immersing or spraying a copper frame supported with barium oxide in a mixed solution containing 20-30% potassium hydroxide and 20-30% yttrium nitrate for 2-5 minutes, filtering immediately after the time is up, calcining the copper frame at 400-500°C for 2-4 hours, cooling, sealing, and packaging to obtain a frame-supported catalyst containing barium oxide, potassium oxide, and yttrium oxide.

[0034] The present invention will be described in further detail below based on specific embodiments.

[0035] Preparation of the reaction vessel before the procedure: The piping for transporting the reaction materials is cleaned, purged, and dried. The reaction vessel is dried until completely dry, cooled to room temperature, and set aside for later use. The following examples illustrate the present invention but do not limit the scope of protection of this patent. In the examples and comparative examples, molecular weight is Mn (number-average molecular weight, measured by gel permeation chromatography GPC), and molecular weight distribution coefficient D (measured by gel permeation chromatography GPC) and polyethylene glycol (PEG) content are measured by liquid chromatography. In the application experiments, surface tension is measured using the method of national standard GB / T5549-2010, and wetting time (penetration force) is measured using the method of national standard GB / T11983-2008.

[0036] Manufacturing of skeletal-supported catalysts: 500g of an aluminum-copper alloy with a particle size of 200-1000μm and a copper-to-aluminum weight ratio of 1:3 was activated in 5L of a 30% potassium hydroxide solution. After 24 hours of activation, the aluminum in the alloy was dissolved in an alkaline solution, filtered, and washed to obtain the copper framework. The copper framework was then placed in 3L of a 17% barium hydroxide aqueous solution at 65°C, slowly cooled to 40°C while slowly stirring, supersaturated with barium hydroxide, and slowly precipitated. The mixture was then filtered to obtain the 200-1000μm copper framework. Copper frame particles with barium hydroxide precipitates attached are selected, and the copper frame particles are calcined at 700-800°C for 3 hours to obtain copper frames supported with barium oxide. These copper frames are then immersed in a mixed solution containing 25% potassium hydroxide and 25% yttrium nitrate by mass for 3 minutes. Immediately after the time is up, the copper frames are filtered, and the copper frames are calcined at 400-500°C for 3 hours. After cooling, sealing, and packaging, a framework-supported catalyst containing barium oxide, potassium oxide, and yttrium oxide is obtained. Example 1

[0037] A method for producing aryl alcohol polyoxyethylene ether using a skeletal-supported catalyst includes the following steps.

[0038] 23.3g of S1, a skeletal-supported catalyst, was placed in the reaction vessel. After replacing the air in the vessel three times with N2, 300g of dried and dewatered allyl alcohol was introduced into the reaction vessel. After the addition of allyl alcohol was completed, the temperature was raised to 90°C, and 1255g of dried and dewatered ethylene oxide was continuously added to start the reaction. The reaction temperature was controlled to 90-140°C, and after the addition was completed, the reaction was continued for 1 hour.

[0039] S2. After completing the reaction, the low-boiling product is extracted using a vacuum, then the temperature is lowered to 60°C, filtered, and the raw materials are added to obtain the finished aryl alcohol polyoxyethylene ether. Example 2

[0040] A method for producing aryl alcohol polyoxyethylene ether using a skeletal-supported catalyst includes the following steps.

[0041] S1, 15.5g of the skeletal-supported catalyst was added to the reaction vessel, and the air inside the vessel was replaced three times with N2. Then, 200g of dried and dehydrated allyl alcohol was introduced into the reaction vessel. After the addition of allyl alcohol was completed, the temperature was raised to 90°C, and 1350g of dried and dehydrated ethylene oxide was added to start the reaction. The reaction temperature was controlled to 90-140°C, and after the addition was completed, the reaction was continued for 1 hour.

[0042] S2. After completing the reaction, the low-boiling product is extracted using a vacuum, then the temperature is lowered to 60°C, filtered, and the raw materials are added to obtain the finished aryl alcohol polyoxyethylene ether. Example 3

[0043] A method for producing aryl alcohol polyoxyethylene ether using a skeletal-supported catalyst includes the following steps.

[0044] S1, 30.0 g of the skeletal-supported catalyst was placed in the reaction vessel, and the air inside the vessel was replaced three times using N2. Then, 300 g of the dried and dehydrated aryl alcohol polyoxyethylene ether produced in Example 1 was introduced into the reaction vessel. After the addition of aryl alcohol polyoxyethylene ether was completed, the temperature was raised to 90°C, and 1250 g of dried and dehydrated ethylene oxide was added to start the reaction. The reaction temperature was controlled to 90-140°C, and after the addition was completed, the reaction was continued for 1 hour.

[0045] S2. After completing the reaction, the low-boiling product is extracted using a vacuum, then the temperature is lowered to 60°C, filtered, and the raw materials are added to obtain the finished aryl alcohol polyoxyethylene ether. Example 4

[0046] A method for producing aryl alcohol polyoxyethylene ether using a skeletal-supported catalyst includes the following steps.

[0047] 38.0 g of S1, a skeletal-supported catalyst, was placed in the reaction vessel. After replacing the air in the vessel three times with N2, 200 g of the dried and dehydrated aryl alcohol polyoxyethylene ether produced in Example 1 was introduced into the reaction vessel. After the addition of aryl alcohol polyoxyethylene ether was completed, the temperature was raised to 90°C, and 1350 g of dried and dehydrated ethylene oxide was added to start the reaction. The reaction temperature was controlled to 90-140°C, and after the addition was completed, the reaction was continued for 1 hour.

[0048] S2. After completing the reaction, the low-boiling product is extracted using a vacuum, then the temperature is lowered to 60°C, filtered, and the raw materials are added to obtain the finished aryl alcohol polyoxyethylene ether. Comparative Example 1

[0049] The manufacturing process disclosed in Chinese patent CN202010754807.X is referred to as Comparative Example 1, and the specific steps are as follows:

[0050] 300g of undried and dewatered allyl alcohol is directly added to a purged N2 reaction vessel. After the addition of allyl alcohol is complete, 0.75g of sodium hydride is added and the reaction is carried out. The reaction is completed, and the hydrogen gas produced by the reaction of allyl alcohol and metallic sodium is extracted by vacuum. The temperature is raised to 90°C, and 1255g of undried and dewatered ethylene oxide is continuously added to start the reaction. The reaction temperature is controlled to 90-110°C, and the reaction is carried out for 2 hours after the addition is completed. After the reaction is completed, the low-boiling product is extracted using vacuum, and the temperature is lowered to 70°C to produce crude aryl alcohol polyoxyethylene ether. After releasing 500g of the crude product, 1.3g of glacial acetic acid and the produced aryl alcohol polyoxyethylene ether are added. Comparative Example 2

[0051] The difference between this comparative example and Comparative Example 1 is that the dose of allyl alcohol is 200 g, the dose of sodium hydride is 0.6 g, the dose of ethylene oxide is 1350 g, and the dose of glacial acetic acid is 1.5 g, while all other process conditions are the same as 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 crude aryl alcohol polyoxyethylene ether produced in Comparative Example 1, in the form of 300 g, the amount of sodium hydride is 0.5 g, the amount of ethylene oxide is 1250 g, and the amount of glacial acetic acid is 1.6 g, while the other process conditions are the same as 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 crude aryl alcohol polyoxyethylene ether produced in Comparative Example 1, in the form of 200 g, the amount of sodium hydride is 1.0 g, the amount of ethylene oxide is 1350 g, and the amount of glacial acetic acid is 2.7 g, while the other process conditions are the same as in Comparative Example 1. Comparative Example 5

[0054] The manufacturing method disclosed in Chinese patent CN200910198310.8 is designated as Comparative Example 5, and the specific steps are as follows.

[0055] First, the reactor air is replaced with nitrogen, 196.7 g of undried and dewatered allyl alcohol is added, and 2.0 g of sodium allyl alcohol catalyst is added. The reactor air is replaced with nitrogen again, stirring is started, and the mixture is heated to the set reaction temperature. 500 g of undried and dewatered ethylene oxide is added and the reaction proceeds until the reaction temperature reaches 90-110°C, at which point the reaction is complete. The mixture is then cooled to 60°C, unreacted ethylene oxide and low molecular weight substances are removed by vacuum extraction, the system pressure is maintained at -0.1 to -0.05 MPa, and the time is maintained at 30 min.

[0056] Stirring was started, and at the same time, 2.65 g of sodium allyl alcohol catalyst was added to the reactor, and the inside of the reactor was purged with N2 gas. The mixture was heated to the set reaction temperature, and the reaction was carried out by passing 854 g of ethylene oxide through it, controlling the reaction pressure to 0-0.4 MPa. After the reaction was complete, 3.5 g of the acetic acid neutralization product was added, and after cooling, the product was filtered using a liquid filtration bag with an accuracy of 50 μm to obtain the allyl polyoxyethylene ether product. Comparative Example 6

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

[0058] First, the air in the reactor is replaced with nitrogen, 296.6g of undried and dewatered allyl alcohol is added, and 4.7g of sodium allyl alcohol catalyst is added. The air in the reactor is replaced with nitrogen again, stirring is started, and the mixture is heated to the set reaction temperature. 1250g of undried and dewatered ethylene oxide is added and the reaction proceeds at a reaction temperature of 90-110°C. The reaction is completed, and the temperature is cooled to 60°C to release 1301g of material.

[0059] Stirring was started, and at the same time, 1.5 g of sodium allyl alcohol catalyst was added to the reactor, and the gas in the reactor was replaced with N2. The mixture was heated to the set reaction temperature, and 1050 g of ethylene oxide was passed through to carry out the reaction, while the reaction pressure was controlled to 0-0.4 MPa. After the reaction was complete, 1.7 g of the acetic acid neutralization product was added, and after cooling, the product was filtered using a liquid filtration bag with an accuracy of 50 μm to obtain the allyl polyoxyethylene ether product.

[0060] 1. Performance comparison test of allyl polyoxyethylene ether

[0061] For the finished allyl polyoxyethylene ether products produced in Examples 1-4 and Comparative Examples 1-6, the polyethylene glycol content (a by-product), the Na+ and K+ content, and the average molecular weight and molecular weight distribution were measured, 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 JPEG0007912273000002.jpg39164

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

[0064] 2. Performance testing of allyl polyoxyethylene ether

[0065] The finished allyl polyoxyethylene ether products 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 allyl polyoxyethylene ether products produced in Examples 1-4 and Comparative Examples 1-6, which are hydrogen-containing silicone oils with a hydrogen content of 0.16%, and the mass concentration is a 1% chlorplatinic acid ethanol solution.

[0067] Synthesis process: The measured aryl alcohol polyoxyethylene ether and hydrogen-containing silicone oil were placed in a reaction vessel, the air inside the vessel was replaced with N2, and the temperature was raised while stirring until it reached 90°C, after which it was stably maintained at 90°C for 5 minutes. The holding time was maintained until the catalyst chloroplatinic acid was added, at which point the heating was stopped, and the highest temperature during the reaction and during the reaction process was recorded and observed. After 30 minutes of reaction, the raw materials were added. The appearance of the finished polyether-modified silicone oil was observed, and the surface tension and penetration force of the finished polyether-modified silicone oil were measured. The results are shown in Table 2 and Figures 1 to 4.

[0068] Table 2: Performance comparison results of finished polyether-modified silicone oil products JPEG0007912273000003.jpg172164

[0069] As can be seen from Table 2 and Figures 1 to 4, polyether-modified silicone oil was synthesized using aryl alcohol polyoxyethylene ether with the same raw material ratio and design and molecular weight, using the same amount of chloroplatinic acid catalyst and hydrogen-containing silicone oil. The polyether-modified silicone oil products synthesized using the aryl alcohol polyoxyethylene ether produced in Examples 1 to 4 were all transparent liquids, but the polyether-modified silicone oil products synthesized using the aryl alcohol polyoxyethylene ether produced in Comparative Examples 1 to 6 were all milky white and layered. This explains that the aryl alcohol polyoxyethylene ether produced in the present invention reacts completely with hydrogen-containing silicone oil to form a transparent liquid, but the reaction in Comparative Examples 1 to 6 was not complete, resulting in a layered, milky white, heterogeneous solution. As can be seen from the maximum temperature of the reaction process, the maximum temperature of the aryl alcohol polyoxyethylene ether reaction process in the present invention is 115°C or higher, explaining that the overall material temperature rises due to the generation of a large amount of reaction heat. However, the maximum temperature of the aryl alcohol polyoxyethylene ether reaction process in Comparative Examples 1 to 6 was 90°C at the start, indicating that the reaction heat is not clear, and that there is basically no reaction, and the temperature does not rise. The surface tension of the polyether-modified silicone oils produced in Examples 1-4 was significantly lower than that of Comparative Examples 1-6, and their surface activity was significantly improved compared to Comparative Examples 1-6 (lower surface tension indicates stronger surface activity). In terms of wetting time, the polyether-modified silicone oils synthesized using aryl alcohol polyoxyethylene ether obtained in Examples 1-4 were similarly significantly shorter than the polyether-modified silicone oils synthesized using aryl alcohol polyoxyethylene ether produced in Comparative Examples 1-6. The polyether-modified silicone oils synthesized in Comparative Examples 1-6 all exceeded 5 minutes and did not exhibit relatively clear wetting power, while the polyether-modified silicone oils synthesized using aryl alcohol polyoxyethylene ether produced in Examples 1-4 had a wetting time of 30 seconds or less.Based on the above, the aryl alcohol polyoxyethylene ether produced by the manufacturing method of the present invention can be suitably applied to the synthesis of polyether-modified silicone oils in fields such as high-end coatings.

[0070] The embodiments described above are merely preferred embodiments of the present invention and do not limit the scope of protection of the present invention. Any substantial changes and substitutions made by those skilled in the art based on the present invention fall within the scope of protection required by the present invention.

Claims

1. A skeletal-supported catalyst, Barium oxide, potassium oxide, and yttrium oxide are supported within a copper frame as catalysts. A skeletal-supported catalyst characterized in that, of which, the weight percentage of the copper frame in the skeletal-supported catalyst is 70 to 90%, and the ratio of the amounts of the barium, potassium, and yttrium elements is 1:0.02 to 0.08:0.01 to 0.

04.

2. The fact that the aforementioned barium oxide, potassium oxide, and yttrium oxide were supported within the copper frame means that Step A: The aluminum-copper alloy is activated in a potassium hydroxide solution for 20-28 hours to dissolve the aluminum in the alloy, then filtered and washed with water to obtain a copper frame. Step B: Place the copper framework in a barium hydroxide aqueous solution at 60-70°C, slowly cool to 35-45°C while stirring slowly, allow barium hydroxide to supersaturate and precipitate, filter the copper framework particles to which the barium hydroxide precipitate has adhered, and calcine the copper framework particles at 700-800°C for 2-4 hours to obtain a copper framework supported with barium oxide. Step C: The method for producing a skeleton-supported catalyst according to claim 1, comprising: immersing or spraying the copper framework supported with barium oxide with a mixed solution containing potassium hydroxide and yttrium nitrate for 2 to 5 minutes; filtering the mixture; firing the copper framework at 400 to 500°C for 2 to 4 hours; and after cooling, supporting barium oxide, potassium oxide, and yttrium oxide within the copper framework.

3. The method for producing a skeleton-supported catalyst according to claim 2, characterized in that the weight ratio of copper to aluminum in the aluminum-copper alloy in step A is 1:2 to 4, and the mass concentration of the potassium hydroxide solution is 25 to 35%.

4. The method for producing a skeleton-supported catalyst according to claim 2, characterized in that the particle size of the aluminum-copper alloy in step A and the particle size of the copper framework particles in step B are both 200 to 1000 μm.

5. The method for producing a skeleton-supported catalyst according to claim 2, characterized in that the mass concentration of the barium hydroxide aqueous solution in step B is 15 to 20%.

6. The method for producing a skeleton-supported catalyst according to claim 2, characterized in that 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%.

7. A method for producing aryl alcohol polyoxyethylene ether using a skeleton-supported catalyst as described in claim 1 is: S1: The skeletal-supported catalyst is placed in a reaction vessel, nitrogen is added to the vessel, then allyl alcohol or aryl alcohol polyoxyethylene ether with a molecular weight of 100 to 600 is added to the reaction vessel, the temperature is raised, and the reaction is continued by passing dried ethylene oxide through it. S2: A method for producing aryl alcohol polyoxyethylene ether, characterized by comprising lowering the temperature, filtering, removing the raw materials after the reaction is completed, and producing the finished aryl alcohol polyoxyethylene ether.

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

9. The method for producing aryl alcohol polyoxyethylene ether according to claim 7, characterized in that in step S2, the temperature is lowered to 55-75°C, then filtered, and the raw material is obtained.

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

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