Preparation method of leveling agent O
Through the preparation of magnesium, aluminum, cobalt composite oxide catalyst and autoclave reaction, the problems of catalyst deactivation and high cost in the preparation of existing uniform dye O are solved, and the catalyst recovery and high purity of products are achieved, which is suitable for industrial production.
Patent Information
- Application Number
- CN202411449273.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-17
- Publication Date
- 2025-01-03
AI Technical Summary
In the existing preparation method of homogenizing agent O, the catalyst has high temperature and inactivation problems, and lithium oxide is expensive and cannot be recycled, which affects the application in other fields.
Magnesium, aluminum, cobalt composite oxide is used as catalysts and prepared by calcining and crushing, combining the vacuum environment and segmented reaction in the autoclave to ensure sufficient reaction and purity of the product.
The recovery and recycling of catalysts are realized, the cost of raw materials is reduced, and the purity and industrial applicability of the products are improved.
Smart Images
Figure CN119241832A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to a method for preparing a leveling agent O, in particular to the preparation of a magnesium-aluminum-cobalt composite oxide, and a method for preparing the leveling agent O by using the composite oxide as a catalyst. Background Art
[0002] Leveling agent O is widely used in textile printing and dyeing, daily chemical, and cosmetics industries as a dispersant, leveling agent, and emulsifier. Industrial production mainly uses C16~C18 fatty alcohol as raw material, KOH, NaOH, etc. as catalyst, and ethylene oxide (abbreviated as: EO) to generate leveling agent O through addition reaction. The main preparation method is as follows: 1. The document "Research on Catalysts for Synthesizing Narrow Distribution Fatty Alcohol Polyoxyethylene Ethers" (Petrochemical Industry, 2001, Vol. 30, No. 11, 847-849) reported a method for preparing lauryl alcohol polyoxyethylene ether using alkoxy metals such as sodium laurate, calcium, and barium as catalysts. The catalyst in this method has problems such as high reaction initiation temperature, long induction period, and easy deterioration and deactivation of alkoxy metal compounds after contact with air.
[0003] 2. Patent CN111378112B provides a method for producing cosmetic-grade leveling agent O by using a complex of lithium oxide and sodium methoxide as a catalyst, reacting natural straight-chain C16~C18 fatty alcohols with ethylene oxide in a polymerization reactor. The lithium oxide used in this method is expensive and cannot be recycled. Lactic acid needs to be added during post-treatment to adjust the pH value. The residual lithium and sodium ions affect the application in other fields.
[0004] 3. The document "Fat Alcohol Polyoxyethylene Ether and Ethoxylation Technology" (China Daily Chemical Industry, 1995, Vol. 20, No. 141, 184-192) briefly introduces the use of strontium, barium oxides and hydroxides, calcium, magnesium carboxylates and other alkaline earth metals as main catalysts, and the addition of phenols or phosphorus-containing compounds as co-catalysts. The development of new catalysts has practical value for improving domestic ethoxylation technology.
[0005] According to literature reports, the present invention provides a method for preparing a leveling agent O using a magnesium-aluminum-cobalt composite oxide as a catalyst. The catalyst can be recycled and reused, thereby reducing the cost of raw materials. Summary of the invention
[0006] The technical problem to be solved by the present invention is to provide a method for preparing a leveling agent, and a method for generating a leveling agent O by reacting C16-18 alcohol and ethylene oxide as raw materials under the action of a catalyst.
[0007] A method for preparing a leveling agent O, characterized in that: The production process includes the following: 1. Preparation method of magnesium-aluminum-cobalt composite oxide catalyst: Step 1: Synthesis; A total of 100 g of metal acetates in different proportions were dried and then crushed in a grinder; Step 2: roasting; The white powder was calcined in a muffle furnace to obtain a catalyst; 2. Preparation method of leveling agent O: Step 1: Feeding; Add C16~18 alcohol and magnesium aluminum cobalt composite oxide catalyst into a 5000ml stainless steel autoclave, and after the feeding is completed, create a vacuum environment inside the stainless steel autoclave; Step 2: Segmented reaction process; Add 100g of ethylene oxide. After the reaction is initiated normally, continue to drop ethylene oxide, remove the reaction heat with cooling water, and keep warm after the addition is completed; Step 3: Filter; After the cooling is completed, the vacuum state inside the stainless steel autoclave is released, the temperature is lowered to 80°C, filtered while hot, and the filtrate is taken to obtain the leveling agent. The filter cake is the catalyst and is applied to the next batch.
[0008] Preferably, the metal acetate mentioned in step 1 of the preparation method of the magnesium-aluminum-cobalt composite oxide catalyst is one or more of magnesium acetate tetrahydrate, basic aluminum acetate, and cobalt acetate tetrahydrate.
[0009] Through the above technical scheme, the above metal salts or metal salt mixtures can achieve the purpose of preparing catalysts.
[0010] Preferably, the drying step mentioned in step 1 of the preparation method of the aluminum-cobalt composite oxide catalyst needs to be dried at 80° C. for 1 hour.
[0011] Through the above technical solution, sufficient reaction can be ensured and the purity of the product can be improved.
[0012] Preferably, the filter cake in step 2 of the method for preparing the magnesium-aluminum-cobalt composite oxide catalyst can be applied to the next batch of reactions.
[0013] Through the above technical solution, the material cost required for production can be reduced, and the reusable catalyst is also beneficial to the stability of the preparation process.
[0014] Preferably, the calcination step mentioned in step 2 of the preparation method of the magnesium-aluminum composite oxide catalyst needs to be calcined at 300° C.-550° C. for 4 hours-6 hours.
[0015] Through the above technical solution, sufficient reaction can be ensured and the purity of the product can be improved. At the same time, high temperature can remove some impurities.
[0016] Preferably, the masses of the C16~18 alcohol and the magnesium-aluminum-cobalt composite oxide catalyst mentioned in step 1 of the preparation method of the leveling agent are 500 g of the C16~18 alcohol and 20 g of the magnesium-aluminum-cobalt composite oxide catalyst, respectively.
[0017] Through the above technical solution, it can be ensured that the input materials can react to the greatest extent under the material ratio conditions, avoiding waste caused by excessive material input, or insufficient reaction caused by insufficient input materials, which leads to reduced product quality.
[0018] Preferably, the vacuum environment formed inside the stainless steel autoclave mentioned in step 1 of the preparation method of leveling agent O needs to be replaced with nitrogen at least 3 times before the autoclave is evacuated to a vacuum degree of -0.095 MPa.
[0019] Through the above technical solution, multiple inert gas passes can ensure that there is no other gas in the kettle to interfere with the reaction process.
[0020] Preferably, after the reaction mentioned in step 2 of the preparation method of leveling agent O is normally initiated, the mass of ethylene oxide continuously added dropwise is 2100 g.
[0021] Through the above technical solution, continuous dripping of materials ensures that the reaction proceeds fully, avoiding waste caused by excessive material input, or insufficient material input leading to inadequate reaction and reduced product quality.
[0022] Preferably, in the step 2 of the preparation method of the leveling agent O, the reaction temperature needs to be controlled at 130-170° C., and the reaction pressure needs to be controlled at ≤0.4 MPa.
[0023] Through the above technical solution, the reaction efficiency can be guaranteed to the greatest extent.
[0024] Preferably, the heat preservation step described in step 2 of the method for preparing the leveling agent O requires aging at 140° C. for 30 minutes.
[0025] Through the above technical solution, the complete reaction process and sufficient reaction can be ensured.
[0026] Compared with the prior art, the present invention has the following advantages: 1. The preparation method of the leveling agent O has a simple process, the catalyst can be recycled and reused, and it is easy to handle.
[0027] 2. The catalyst mentioned in the preparation method of the leveling agent O has good selectivity, and the prepared leveling agent O has a narrow molecular weight distribution, low color, and few by-products.
[0028] 3. The catalyst mentioned in the preparation method of the leveling agent O is simple to prepare, low in cost, and suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS
[0029] Figure 1 It is a schematic diagram of the process of the present invention. DETAILED DESCRIPTION
[0030] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0031] See also Figure 1 The present invention provides a technical solution: a method for preparing a leveling agent O.
[0032] Specific: Method 1: A method for preparing a magnesium-aluminum-cobalt composite oxide catalyst with a magnesium-aluminum-cobalt ratio of 2:1:2, using magnesium acetate tetrahydrate, basic aluminum acetate and cobalt acetate tetrahydrate in different mass ratios as raw materials, and sequentially performing the following steps: Step 1: Synthesis; Put 100 g of magnesium acetate tetrahydrate, basic aluminum acetate, and cobalt acetate tetrahydrate in different mass ratios (abbreviated as magnesium aluminum cobalt ratio or Mg:Al:Co) = 2:1:2 in an oven at 80°C for 1 hour, take out and grind in a grinder; Step 2: roasting; The white powder is calcined in a muffle furnace at 300-550°C for 4-6 hours to obtain a catalyst.
[0033] Embodiment 1: A magnesium-aluminum-cobalt composite oxide catalyst with a magnesium-aluminum-cobalt ratio of 2:1:2 (prepared by the above method 1) is used to prepare a leveling agent O using C16-18 alcohol as a starter and ethylene oxide as a starting material, and the following steps are performed in sequence: Step 1: Feeding; Add 500g of C16~18 alcohol and 20g of the catalyst prepared in method 1 into a 5000ml stainless steel autoclave, replace the air in the autoclave with nitrogen for 3 times, heat to 120℃ and evacuate to a vacuum degree of -0.095Mpa; Step 2: Segmented reaction process; Add 100g of ethylene oxide. After the reaction is initiated normally, continuously add 2100g of ethylene oxide dropwise. Remove the reaction heat with cooling water. Control the reaction temperature at 130-170°C and the reaction pressure ≤0.4MPa. After the addition is completed, keep the temperature at 140°C for 30min. Step 3: Filter; Cool down to 80℃, drain, filter while hot, take the filtrate to get the leveling agent, and use the filter cake as a catalyst for the next batch. After testing, the hydroxyl value is 41.6mgKOH / g, the cloud point (10% sodium chloride aqueous solution): 95.4℃, the molecular weight distribution number (abbreviation: Mw / Mn): 1.05, the color (10% aqueous solution, Pt-Co): 10, and the dioxane mg / kg: not detected.
[0034] Embodiment 2~embodiment 6: The amount of catalyst, reaction time and reaction temperature in Example 1 were changed (as shown in Table 2); the rest was the same as Example 1, thus obtaining Examples 2 to 6. The obtained leveling agent O is shown in Table 1.
[0035] Table 1 Example Catalyst dosage / g Reaction temperature / ℃ Reaction time / h Hydroxyl value mgKOH / g Cloud point / ℃ Mw / Mn Color Dioxane mg / kg 1 20 140 4 41.6 95.4 1.05 10 Not detected 2 40 140 3.5 41.4 95.6 1.08 15 Not detected 3 80 140 2 41.8 95.2 1.10 20 Not detected 4 10 140 8 42.2 94.5 1.04 10 Not detected 5 20 130 5 41.5 95.3 1.05 10 Not detected 6 20 150 3.5 42.8 94.2 1.09 10 0.15 Embodiment 7~embodiment 15: Step 1 of the preparation method of the magnesium-aluminum-cobalt composite oxide catalyst in Method 1 is changed, that is, the magnesium-aluminum-cobalt ratio in Step 1 is changed; and the magnesium-aluminum-cobalt composite oxide catalyst obtained above is used to replace the "magnesium-aluminum composite oxide with a magnesium-aluminum-cobalt ratio of 2:1:2 (obtained in Method 1)" in Example 1 (as shown in Table 2); the rest is the same as Example 1, thereby obtaining Examples 7 to 15. The obtained leveling agent O is shown in Table 2.
[0036] Table 2 Example Magnesium aluminum cobalt ratio (Mg:Al:Co) Catalyst dosage / g Reaction time / h Hydroxyl value mgKOH / g Cloud point / ℃ Mw / Mn Color Dioxane mg / kg 1 2：1：2 20 4 41.6 95.4 1.05 10 Not detected 7 2：2：1 20 5 41.4 95.5 1.06 15 Not detected 8 3：1：1 20 3 41.8 95.2 1.06 10 Not detected 9 1：2：2 20 6 41.9 95.1 1.08 15 Not detected 10 1：3：1 20 7 42.9 94.2 1.09 20 Not detected 11 1：1：3 20 7 42.6 94.5 1.10 20 Not detected 12 1：1：0 20 8 42.8 94.1 1.12 25 0.20 13 1：0：1 20 8 43.8 93.0 1.16 30 0.50 14 1：0：0 20 6 44.5 92.7 1.30 40 0.8 15 0：0：1 20 No reaction —— —— —— —— —— Embodiment 1-1~embodiment 1-5: The filter cake obtained from the previous batch of reactions was used to replace the "20 g of magnesium-aluminum-cobalt composite oxide with a magnesium-aluminum-cobalt ratio of 2:1:2" used in the steps of Example 1; that is, the number of catalyst cycles was changed, and the rest was the same as Example 1; the specific contents and data are shown in Table 3.
[0037] Table 3 Example 1 1-1 1-2 1-3 1-4 1-5 Catalyst cycle times 0 1 2 3 4 5 Reaction time / h 5 5 5 5 5 5 Hydroxyl value mgKOH / g 41.6 41.8 41.2 41.5 41.6 41.5 Cloud point / ℃ 95.4 95.2 95.6 95.4 95.4 95.4 Mw / Mn 1.05 1.06 1.09 1.07 1.06 1.08 Color (Pt-Co) 10 11 10 10 12 10 Dioxane mg / kg Not detected Not detected Not detected Not detected Not detected Not detected Comparative Example 1-1~Comparative Example 1-5: The "20 g of catalyst prepared in method 1" in step 2 is replaced with sodium hydroxide, 30% sodium methoxide methanol solution, potassium hydroxide, and lithium hydroxide; the rest is the same as in Example 1, thereby obtaining Comparative Examples 1-1 to Comparative Examples 1-5. The obtained leveling agent O is shown in Table 4.
[0038] Table 4 Comparative Example catalyst Catalyst dosage / g Reaction time / h Hydroxyl value mgKOH / g Cloud point / ℃ Mw / Mn Color Dioxane mg / kg 1-1 Sodium hydroxide 8 3 42.5 94.5 1.30 40 30 1-2 Sodium methoxide solution 20 2.5 42.2 94.8 1.35 30 26 1-3 Potassium hydroxide 8 2.5 42.8 94.2 1.25 30 22 1-4 Lithium hydroxide 7 4 42.4 94.6 1.20 30 15 1-5 Barium Hydroxide 10 6 41.8 95.2 1.15 20 8 In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of the present invention, the meaning of "plurality" is two or more, unless otherwise clearly and specifically defined.
[0039] What is described above is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.
Claims
1. A method for preparing a leveling agent O, characterized in that: The production process includes the following:
1. Preparation method of magnesium-aluminum-cobalt composite oxide catalyst: Step 1: Synthesis; A total of 100 g of metal acetates in different proportions were dried and then crushed in a grinder; Step 2: roasting; The white powder was calcined in a muffle furnace to obtain a catalyst; 2. Preparation method of leveling agent O: Step 1: Feeding; Add C16~18 alcohol and magnesium aluminum cobalt composite oxide catalyst into a 5000ml stainless steel autoclave, and after the feeding is completed, create a vacuum environment inside the stainless steel autoclave; Step 2: Segmented reaction process; Add 100g of ethylene oxide. After the reaction is initiated normally, continue to drop ethylene oxide, remove the reaction heat with cooling water, and keep warm after the addition is completed; Step 3: Filter; After the cooling is completed, the vacuum state inside the stainless steel autoclave is released, the temperature is lowered to 80°C, filtered while hot, and the filtrate is taken to obtain the leveling agent O. The filter cake is used as a catalyst and is applied to the next batch.
2. The method for preparing a leveling agent O according to claim 1, characterized in that: The metal acetate mentioned in step 1 of the preparation method of the magnesium-aluminum-cobalt composite oxide catalyst is one or more of magnesium acetate tetrahydrate, basic aluminum acetate, and cobalt acetate tetrahydrate.
3. The method for preparing a leveling agent O according to claim 1, characterized in that: The drying step mentioned in step 1 of the preparation method of the magnesium-aluminum-cobalt composite oxide catalyst needs to be dried at 80° C. for 1 hour.
4. The method for preparing a leveling agent O according to claim 1, characterized in that: The filter cake in step 2 of the preparation method of the magnesium-aluminum-cobalt composite oxide catalyst can be applied to the next batch of reactions.
5. The method for preparing a leveling agent O according to claim 1, characterized in that: The calcination step mentioned in step 2 of the preparation method of the magnesium-aluminum composite oxide catalyst needs to be calcined at 300° C.-550° C. for 4 hours-6 hours.
6. The method for preparing a leveling agent O according to claim 1, characterized in that: The masses of the C16~18 alcohol and the magnesium-aluminum-cobalt composite oxide catalyst mentioned in step 1 of the preparation method of the leveling agent O are 500g of the C16~18 alcohol and 20g of the magnesium-aluminum-cobalt composite oxide catalyst, respectively.
7. The method for preparing a leveling agent O according to claim 1, characterized in that: The vacuum environment formed inside the stainless steel autoclave mentioned in step 1 of the preparation method of the leveling agent O needs to be replaced with nitrogen at least 3 times before the autoclave is evacuated to a vacuum degree of -0.095 MPa.
8. The method for preparing a leveling agent O according to claim 1, characterized in that: After the reaction mentioned in step 2 of the preparation method of the leveling agent O is normally initiated, the mass of ethylene oxide added dropwise continuously is 2100 g.
9. The method for preparing a leveling agent O according to claim 1, characterized in that: In the step 2 of the preparation method of the leveling agent O, the reaction temperature needs to be controlled at 130-170° C., and the reaction pressure needs to be controlled at ≤0.4 MPa.
10. The method for preparing a leveling agent O according to claim 1, characterized in that: The heat preservation step in step 2 of the preparation method of the leveling agent O requires aging at 140° C. for 30 minutes.