Preparation method and application of low-foam multi-block polyether

Abstract

The invention belongs to the technical field of synthesis of ether compounds, and discloses a preparation method and application of low-foam multi-block polyether. The preparation method comprises the following steps: mixing an initiator with a basic catalyst, heating, dropwise adding first ethylene oxide, and carrying out primary reaction and primary curing; after the primary curing is finished, adding epoxide to carry out secondary reaction and secondary curing; after the secondary curing is finished, adding second ethylene oxide to carry out third reaction and third curing; and finally, degassing and neutralizing to prepare the low-foam multi-block polyether. The second ethylene oxide accounts for 25-55% of the total mass of the first ethylene oxide and the second ethylene oxide; the epoxide comprises propylene oxide, a mixture of ethylene oxide and propylene oxide, or a propylene oxide-ethylene oxide-propylene oxide block structure. The multi-block polyether prepared by the invention not only can meet the working temperature of wet cleaning of chips, but also has the advantages of few byproducts, low foaming and excellent defoaming performance.

Description

Technical Field

[0001] The invention belongs to the technical field of ether compound synthesis, and particularly relates to a preparation method of a low-foam multi-block polyether and application thereof. Background Art

[0002] Some organic and inorganic compounds are required in the manufacturing process of chips. The manufacturing process has always been carried out in clean rooms, but there is human intervention, which leads to various environmental contamination of wafers. Contaminants are divided into four categories according to their existence: particulate matter, organic matter, metal contaminants and oxides. Human skin oil, clean room air, machine oil, silicone vacuum grease, photoresist, cleaning solvents and other organic contaminants can be found in chip processes. Each contaminant affects the process in different ways, but mainly by creating an organic layer that prevents the cleaning solution from reaching the wafer surface. Therefore, removing organic matter is usually the first step in cleaning. Wet cleaning is usually used to remove chip organic matter.

[0003] The polyether used for wet cleaning of chips needs to meet the following requirements: 1. Good cleaning performance and can effectively remove organic impurities. 2. No solid particles. Solid particles will adhere to or wear the silicon surface during the cleaning process, affecting the geometric characteristics and electrical performance development of subsequent processes. 3. Low foam. Excessive foam during the cleaning process will lead to reduced cleaning efficiency and poor cleaning effect. 4. The working temperature is 20-30℃.

[0004] In order to meet the above requirements, the initiator uses a fatty alcohol or isomeric alcohol with a carbon number between 10-18, an EO ratio of 40%-60%, and a molecular weight of less than 1000. After the three conditions are determined, it is still difficult for the diepoxide block to meet the working temperature requirements. In addition, in the catalytic process, inorganic base catalysis easily leads to the production of small molecules in the PO reaction stage, resulting in polyether byproducts with high EO content in the product, which will significantly affect the foaming performance of the product; even if the heterogeneous solid acid and solid base catalysts are filtered, it is difficult to completely avoid particle residues; organic base catalysts have poor catalytic effect on the epoxidation reaction of monofunctional initiators. Therefore, it is still necessary to study the catalyst so that it can both ensure the catalytic effect and avoid the formation of small molecule byproducts in the PO segment, so that the prepared polyether has good foaming performance. Summary of the invention

[0005] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention provides a method for preparing a low-foam multi-block polyether and its application. The multi-block polyether prepared by the present invention has less small molecule byproducts, low foaming, excellent defoaming performance, and can meet the working temperature of chip wet cleaning.

[0006] The invention provides a method for preparing low-foam multi-block polyether.

[0007] Specifically, a method for preparing a low-foam multi-block polyether comprises the following steps:

[0008] The initiator and the alkaline catalyst are mixed, and after heating, the first ethylene oxide is added dropwise for a primary reaction and a primary aging; after the primary aging is completed, the epoxide is added for a secondary reaction and a secondary aging; after the secondary aging is completed, the second ethylene oxide is added for a tertiary reaction and a tertiary aging; finally, after degassing and neutralization, a low-foam multi-block polyether is obtained;

[0009] The second ethylene oxide accounts for 25% to 55% of the total mass of the first ethylene oxide and the second ethylene oxide;

[0010] The epoxide includes propylene oxide, a mixture of ethylene oxide and propylene oxide, and a propylene oxide-ethylene oxide-propylene oxide block structure.

[0011] In some embodiments of the present invention, the second ethylene oxide accounts for 30%-50% of the total mass of the first ethylene oxide and the second ethylene oxide.

[0012] In some embodiments of the present invention, the initiator is a fatty alcohol or isomeric alcohol having a carbon atom chain of 10 to 18, such as isodecanol, dodecanol, isoundecanol, isotridecanol, tetradecanol, isohexadecanol, C16-18 alcohol, isostearyl alcohol, and the like.

[0013] In some embodiments of the present invention, the alkaline catalyst includes a first alkaline catalyst and a second alkaline catalyst, wherein the first alkaline catalyst is selected from at least one of sodium hydroxide, potassium hydroxide, sodium methoxide, and potassium methoxide; and the second alkaline catalyst is selected from at least one of tetramethylguanidine (TMG), 1,8-diazacyclo[5,4,0]undecene-7 (DBU), and triethylamine. When the initiator is a fatty alcohol or isomeric alcohol with a shorter molecular chain, mixing and adding the first alkaline catalyst and the second alkaline catalyst can not only reduce and avoid the formation of small molecular byproducts in the PO segment, but also significantly improve the defoaming performance.

[0014] In some embodiments of the present invention, the mixing process of the initiator and the alkaline catalyst is: firstly mix the initiator and the first alkaline catalyst, dehydrate them at 80-120°C and a vacuum degree of -0.098Mpa for 20-180min; then cool them to 40-60°C and add the second alkaline catalyst.

[0015] In some embodiments of the present invention, the input amount of the first alkaline catalyst is 0.05%-1% of the mass of the low-foam multi-block polyether.

[0016] In some embodiments of the present invention, the input amount of the second alkaline catalyst is 0.05%-1% of the mass of the low-foam multi-block polyether.

[0017] In some embodiments of the present invention, the reaction temperature of the primary reaction is 140° C.-170° C.; the temperature of the primary aging is 80-140° C.; and the time of the primary aging is 60-300 min.

[0018] In some embodiments of the present invention, the reaction temperature of the secondary reaction is 140° C.-170° C.; the temperature of the secondary aging is 80-140° C.; and the time of the secondary aging is 60-300 min.

[0019] In some embodiments of the present invention, the reaction temperature of the three reactions is 140° C.-170° C.; the temperature of the three agings is 80-140° C.; and the time of the three agings is 60-300 min.

[0020] In some embodiments of the present invention, the neutralization process is: cooling the reaction system to 60-65° C. and then adding acid solution for neutralization.

[0021] In some embodiments of the present invention, the acid solution is at least one of formic acid, acetic acid, isooctanoic acid, and isononanoic acid. The amount of the acid solution added is 0.5-1.5 of the molar number of the alkaline catalyst.

[0022] The invention also provides a low-foam multi-block polyether.

[0023] Specifically, a low-foam multi-block polyether is prepared by the above preparation method, and the structure of the low-foam multi-block polyether is initiator-EO-X-EO, wherein X is a PO segment, an EO / PO random segment or a PO-EO-PO block.

[0024] The present invention also provides application of the low-foam multi-block polyether.

[0025] Specifically, the low-foam multi-block polyether is used in the preparation of a chip cleaning agent.

[0026] Fatty alcohol or isomeric alcohol polyethers with carbon atoms of 10-18 have good cleaning performance, but application conditions often limit their application in more industries. The present invention uses a multi-block approach and controls the ratio of each block to make the cloud point of the prepared polyether between 20-30°C, which can meet the ideal working temperature for wet cleaning of chips; and the obtained polyether has few small molecule by-products and excellent defoaming performance, which can broaden its use conditions and be applied to chip cleaning.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] (1) The present invention adjusts the block structure to be initiator-EO-X-EO, the polyether ends with an EO segment, X is a PO segment, an EO / PO random segment or a PO-EO-PO block, and controls the proportion of the polyether tail EO to the total EO to be 30%-50%, so that the prepared multi-block polyether can not only meet the working temperature of chip wet cleaning, but also has less by-products, low foaming, and excellent defoaming performance.

[0029] (2) The method for preparing the low-foam multi-block polyether provided by the present invention has a reasonable process, simple operation, and a stable product. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a comparison diagram of the liquid phase and liquid quality of the multi-block polyether prepared in Example 1 and Comparative Example 2. DETAILED DESCRIPTION

[0031] In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the following embodiments are listed for illustration. It should be pointed out that the following embodiments do not limit the protection scope of the present invention.

[0032] Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0033] Example 1

[0034] A method for preparing a low-foam multi-block polyether (isomeric decanol multi-block polyether), comprising the following steps:

[0035] 158g of isodecanol and 0.57g of potassium hydroxide were put into a reactor and dehydrated for 60min at a temperature of 85°C and vacuum-0.098Mpa; the dehydrated initiator was cooled to 50°C, 0.81g of DBU was added, the mixture was fully stirred and mixed, and nitrogen was placed; the reaction temperature was then raised to 155°C, and 233g of ethylene oxide was added dropwise for reaction; after the addition of ethylene oxide was completed, the temperature was immediately lowered to 130°C for aging, and the aging time was 60min; after the aging was completed, the temperature was raised to 155°C, and 293g of propylene oxide was added dropwise for reaction; after the addition of propylene oxide was completed, the temperature was immediately lowered to 130°C for aging, and the aging time was 180min; after the aging was completed, the temperature was raised to 155°C, and 126g of ethylene oxide was added dropwise for reaction; after the addition of ethylene oxide was completed, the temperature was immediately lowered to 130°C for aging, and the aging time was 60min. Finally, degassing was performed at 100°C for 20 min. After degassing, the temperature was lowered to 60-65°C, and 0.71 g of formic acid was added dropwise for neutralization. After neutralization, the material was discharged at 60°C to obtain a low-foaming multi-block polyether.

[0036] Comparative Example 1

[0037] A method for preparing a multi-block polyether (isomeric decanol multi-block polyether), comprising the following steps:

[0038] 158g of isodecanol and 0.57g of potassium hydroxide were put into a reactor and dehydrated at 85°C under vacuum-0.098Mpa for 60min; the dehydrated initiator was cooled to 50°C, 0.81g of DBU was added, the mixture was fully stirred and mixed, and nitrogen was placed; the temperature was then raised to 155°C, and 293g of propylene oxide was added dropwise for reaction; after the addition of propylene oxide was completed, the temperature was immediately lowered to 130°C for aging, and the aging time was 180min; after the aging was completed, the temperature was raised to 155°C, and 359g of ethylene oxide was added dropwise for reaction; after the addition of ethylene oxide was completed, the temperature was immediately lowered to 130°C for aging, and the aging time was 60min; finally, degassed at 100°C for 20min; after the degassed was completed, the temperature was lowered to 60-65°C, 0.71g of formic acid was added dropwise for neutralization; after the neutralization was completed, the material was discharged at 60°C to obtain a multi-block polyether.

[0039] Comparative Example 2

[0040] A method for preparing a multi-block polyether (isomeric decanol multi-block polyether), comprising the following steps:

[0041] 158g of isodecanol and 0.86g of potassium hydroxide were put into a reactor and dehydrated at 85°C under vacuum-0.098Mpa for 60min; then the reaction temperature was raised to 155°C and 233g of ethylene oxide was added dropwise for reaction; after the addition of ethylene oxide was completed, the temperature was immediately lowered to 130°C for aging for 60min; after the aging was completed, the temperature was raised to 155°C and 293g of propylene oxide was added dropwise for reaction; after the addition of propylene oxide was completed, The temperature was immediately lowered to 130°C for aging for 180 minutes; after aging, the temperature was raised to 155°C, and 126g of ethylene oxide was added dropwise for reaction; after the addition of ethylene oxide was completed, the temperature was immediately lowered to 130°C for aging for 60 minutes; finally, degassing was performed at 100°C for 20 minutes; after degassing, the temperature was lowered to 60-65°C, and 0.71g of formic acid was added dropwise for neutralization; after neutralization, the material was discharged at 60°C to obtain a multi-block polyether.

[0042] Comparative Example 3

[0043] A method for preparing a multi-block polyether (isomeric decanol multi-block polyether), comprising the following steps:

[0044] 158g of isodecanol and 0.57g of potassium hydroxide were put into a reactor and dehydrated at 85°C under vacuum-0.098Mpa for 60min; the dehydrated initiator was cooled to 50°C, 0.81g of DBU was added, the mixture was fully stirred and nitrogen was placed; the reaction temperature was then raised to 155°C, and 287g of ethylene oxide was added dropwise for reaction; after the addition of ethylene oxide was completed, the temperature was immediately lowered to 130°C for aging, and the aging time was 60min; after the aging was completed, the temperature was raised to 155°C, and 293g of Propylene oxide is reacted; after the addition of propylene oxide is completed, the temperature is immediately reduced to 130°C for aging, and the aging time is 180 minutes; after the aging is completed, the temperature is raised to 155°C, and 72g of ethylene oxide is added dropwise for reaction; after the addition of ethylene oxide is completed, the temperature is immediately reduced to 130°C for aging, and the aging time is 60 minutes; finally, degassing is carried out at 100°C for 20 minutes; after the degassing is completed, the temperature is reduced to 60-65°C and 0.71g of formic acid is added dropwise for neutralization; after the neutralization is completed, the material is discharged at 60°C to obtain a multi-block polyether.

[0045] Comparative Example 4

[0046] A method for preparing a multi-block polyether (isomeric decanol multi-block polyether), comprising the following steps:

[0047] 158g of isodecanol and 0.57g of potassium hydroxide were put into a reactor and dehydrated at 85°C under vacuum-0.098Mpa for 60min; the dehydrated initiator was cooled to 50°C, 0.81g of DBU was added, the mixture was fully stirred and nitrogen was placed; the reaction temperature was then raised to 155°C, 144g of ethylene oxide was added dropwise to react; after the addition of ethylene oxide was completed, the temperature was immediately lowered to 130°C for aging, and the aging time was 60min; after the aging was completed, the temperature was raised to 155°C, 293g of ethylene oxide was added dropwise, and the reaction mixture was stirred and nitrogen was placed; ... After the addition of propylene oxide is completed, the temperature is immediately lowered to 130°C for aging, and the aging time is 180min; after the aging is completed, the temperature is raised to 155°C, and 215g of ethylene oxide is added dropwise for reaction; after the addition of ethylene oxide is completed, the temperature is immediately lowered to 130°C for aging, and the aging time is 60min; finally, degassing is carried out at 100°C for 20min; after the degassing is completed, the temperature is lowered to 60-65°C and 0.71g of formic acid is added dropwise for neutralization; after the neutralization is completed, the material is discharged at 60°C to obtain a multi-block polyether.

[0048] The multi-block polyether prepared in Example 1 and Comparative Examples 1-4 was subjected to performance tests, including turbidity point (1% water), foam height, time for foam to remain 8 mL (0.5% water / 25°C), and time for foam to remain 5 mL (0.5% water / 25°C). The bubble performance test was conducted by an oscillation method, where each multi-block polyether was prepared into a 0.5% aqueous solution, 50 mL of the liquid was placed in a stoppered measuring cylinder, and oscillated 20 times at 25°C, then the foam level was observed and the time was recorded. The test results are shown in Table 1.

[0049] Table 1

[0050]

[0051] In practical applications, the ideal cleaning temperature is 20-30 degrees Celsius, so the turbidity point is 20-30℃ for the best working temperature. If the turbidity point is lower than 20℃, the polyether will precipitate within the cleaning temperature range and lose its cleaning function; if it is higher than 30℃, the polyether will be too hydrophilic and will also affect the cleaning ability.

[0052] As can be seen from Table 1, Example 1 and Comparative Example 1 have the same initiator and EO / PO ratio, but the different block structures lead to a huge difference in the cloud point of the 1% aqueous solution of the product, which also causes Comparative Example 1 to fail to meet the working environment above 12.6°C, and the foam performance is slightly worse than that of Example 1. Comparative Examples 3 and 4 have an EO ratio at the end that is not within the range of 30%-50%, and their cloud points also fail to meet the requirements.

[0053] The multi-block polyether prepared in Example 1 and Comparative Example 2 was subjected to liquid phase and liquid mass analysis. Figure 1 The liquid phase and liquid quality comparison diagram of the multi-block polyether prepared in Example 1 and Comparative Example 2. Figure 1 It can be seen that Comparative Example 2 has more small molecule by-products than Example 1, which also leads to high foaming and poor defoaming performance of the obtained multi-block polyether.

[0054] Embodiment 2-9

[0055] Examples 2-9 provide 8 methods for preparing low-foam multi-block polyethers, and their specific parameters such as initiator, dehydration conditions, catalyst used, block structure, reaction temperature, and aging temperature are shown in Table 2:

[0056] Table 2

[0057]

[0058]

[0059] The multi-block polyether prepared in Examples 2-9 was subjected to performance tests, including cloud point (1% water), foam height, time when foam remains 8 mL (0.5% water / 25°C), and time when foam remains 5 mL (0.5% water / 25°C). The test results of Examples 2-9 are shown in Table 3.

[0060] Table 3

[0061]

[0062] As shown in Table 3, the cloud point of the multi-block polyether prepared in Examples 2-9 is 21-30°C, which is the optimal working temperature; the foaming height is less than or equal to 85mL, the foam residue is 8mL within 4min, and the foam residue is 5mL within 8min10s. It has low foaming and excellent defoaming performance. Among them, Examples 7-9 have relatively excellent foaming and defoaming properties without adding organic base catalysis because the carbon chain of the selected initiator is long enough.

[0063] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for preparing a low-foam multi-block polyether, characterized in that: The following steps are involved: The initiator and the alkaline catalyst are mixed, and after heating, the first ethylene oxide is added dropwise for a primary reaction and a primary aging; after the primary aging is completed, the epoxide is added for a secondary reaction and a secondary aging; after the secondary aging is completed, the second ethylene oxide is added for a tertiary reaction and a tertiary aging; finally, after degassing and neutralization, a low-foam multi-block polyether is obtained; The second ethylene oxide accounts for 25% to 55% of the total mass of the first ethylene oxide and the second ethylene oxide; The epoxide comprises propylene oxide, a mixture of ethylene oxide and propylene oxide, or a propylene oxide-ethylene oxide-propylene oxide block structure.

2. The preparation method according to claim 1, characterized in that: The second ethylene oxide accounts for 30%-50% of the total mass of the first ethylene oxide and the second ethylene oxide.

3. The preparation method according to claim 1 or 2, characterized in that: The initiator is a fatty alcohol or an isomeric alcohol having a chain of 10 to 18 carbon atoms.

4. The preparation method according to claim 1 or 2, characterized in that: The alkaline catalyst comprises a first alkaline catalyst and a second alkaline catalyst, wherein the first alkaline catalyst is selected from at least one of sodium hydroxide, potassium hydroxide, sodium methoxide and potassium methoxide; and the second alkaline catalyst is selected from at least one of tetramethylguanidine, 1,8-diazacyclo[5,4,0]undecene-7 and triethylamine.

5. The preparation method according to claim 4, characterized in that: The mixing process of the initiator and the alkaline catalyst is as follows: firstly, the initiator and the first alkaline catalyst are mixed, and dehydrated for 20-180 minutes at 80-120° C. and a vacuum degree of -0.098 MPa; then, the temperature is lowered to 40-60° C., and the second alkaline catalyst is added.

6. The preparation method according to claim 4, characterized in that: The input amount of the first alkaline catalyst is 0.05%-1% of the mass of the low-foam multi-block polyether; the input amount of the second alkaline catalyst is 0.05%-1% of the mass of the low-foam multi-block polyether.

7. The preparation method according to claim 1 or 2, characterized in that: In some embodiments of the present invention, the reaction temperature of the primary reaction is 140°C-170°C; the reaction temperature of the secondary reaction is 140°C-170°C; the reaction temperature of the tertiary reaction is 140°C-170°C.

8. The preparation method according to claim 1 or 2, characterized in that: The temperature of the first aging is 80-140°C, and the time of the first aging is 60-300min; the temperature of the second aging is 80-140°C, and the time of the second aging is 60-300min; the temperature of the third aging is 80-140°C, and the time of the third aging is 60-300min.

9. A low-foam multi-block polyether, characterized in that: The low-foam multi-block polyether is prepared by the preparation method according to any one of claims 1 to 8, and the structure of the low-foam multi-block polyether is initiator-EO-X-EO, wherein X is a PO segment, an EO / PO random segment or a PO-EO-PO block.

10. Use of the low-foam multi-block polyether according to claim 9 in the preparation of a chip cleaning agent.

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