Process for the preparation of a low-foaming multi-block polyether and use thereof

Abstract

The application belongs to the technical field of ether compound synthesis, and discloses a preparation method and application of low-foaming multi-block polyether. The preparation method comprises the following steps: mixing a starter and an alkaline catalyst, adding first ethylene oxide drop by drop for one-time reaction after warming, and one-time curing; adding an epoxide for two-time reaction after one-time curing is completed, and two-time curing; adding second ethylene oxide for three-time reaction after two-time curing is completed, and three-time curing; and finally, the low-foaming multi-block polyether is prepared through degassing and neutralization; the second ethylene oxide accounts for 25%-55% of the total mass of the first ethylene oxide and the second ethylene oxide; and 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 application can not only meet the working temperature of chip wet cleaning, but also has less by-products, low foaming, and excellent defoaming performance.

Description

TECHNICAL FIELD

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

[0002] Some organic and inorganic compounds are needed in the manufacturing process of chips. The manufacturing process has been carried out in a clean room, but there is human intervention, so it can cause various environmental contaminations of wafers. Contaminants are divided into four categories according to their forms: particulate matter, organic matter, metal contaminants and oxides. Human skin oil, clean room air, mechanical oil, silicone vacuum grease, photoresist, cleaning solvent and other organic contaminants can be found in chip processes. Each contaminant affects the process in different ways, but mainly by producing an organic layer to prevent the cleaning solution from reaching the wafer surface. Therefore, the removal of organic matter is usually the first step of cleaning. The removal of chip organic matter usually adopts wet cleaning.

[0003] The polyether used for chip wet cleaning needs to have the following requirements: 1. Good cleaning performance, which can effectively remove organic impurities. 2. No solid particles. Solid particles can adhere to or wear the silicon surface during the cleaning process, affecting the development of geometric characteristics and electrical properties in subsequent processes. 3. Low foam. Too much foam in the cleaning process can cause the cleaning efficiency to be reduced and the cleaning effect to be poor. 4. The working temperature is 20-30 DEG C.

[0004] In order to meet the above requirements, the starting agent is selected to be a fatty alcohol or an isomeric alcohol with a carbon atom number of 10-18, and the EO proportion is 40%-60%, and the molecular weight is less than 1000. After the three conditions are determined, it is still difficult for the double epoxy block to meet the requirement of the working temperature. Moreover, the inorganic base catalysis in the catalytic process is easy to cause small molecules in the PO reaction stage, so that the product has a high EO content, which can obviously affect the foaming performance of the product; the solid acid and solid base catalysts in the heterogeneous phase are difficult to completely avoid the particle residues even after filtration; the organic base catalyst has poor catalytic effect on the epoxidation reaction of the monofunctionality starting agent. Therefore, the catalyst still needs to be researched, so that the catalytic effect can be ensured and the formation of small molecule by-products in the PO stage can be avoided, so that the prepared polyether has good foam performance. SUMMARY

[0005] The present application aims at at least solving one of the technical problems existing in the prior art. To this end, the present application provides a preparation method of low-foam multi-block polyether and application thereof. The multi-block polyether prepared by the present application has less small molecule by-products, low foaming, excellent defoaming performance, and can meet the working temperature of chip wet cleaning.

[0006] The present application provides a preparation method of low-foam multi-block polyether.

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

[0008] The initiator is mixed with the basic catalyst, and after warming, the first reaction is carried out by adding the first ethylene oxide dropwise, and the first curing is carried out; after the first curing is completed, the second reaction is carried out by adding the epoxide, and the second curing is carried out; after the second curing is completed, the third reaction is carried out by adding the second ethylene oxide, and the third curing is carried out; finally, after degassing and neutralization, the low-foam multi-block polyether is prepared.

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

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

[0011] In some embodiments of the present application, 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 application, the initiator is a fatty alcohol or an isomeric alcohol with a chain of 10 to 18 carbon atoms, such as isodecanol, dodecanol, isoundecanol, isotridecanol, tetradecanol, isohexadecanol, C16-18 alcohol, isooctadecanol, and the like.

[0013] In some embodiments of the present application, the basic catalyst comprises a first basic catalyst and a second basic catalyst, the first basic catalyst is selected from at least one of sodium hydroxide, potassium hydroxide, sodium methoxide, and potassium methoxide; and the second basic catalyst is selected from at least one of tetramethylguanidine (TMG), 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU), and triethylamine. When the initiator is a fatty alcohol or an isomeric alcohol with a relatively short molecular chain, the first basic catalyst and the second basic catalyst are mixed, which not only can reduce and avoid the formation of PO segment small molecule byproducts, but also can significantly improve the defoaming performance.

[0014] In some embodiments of the present application, the mixing process of the initiator and the basic catalyst is as follows: first, the initiator is mixed with the first basic catalyst, and then dehydrated at 80-120°C and a vacuum degree of-0.098 Mpa for 20-180 min; and then cooled to 40-60°C, and the second basic catalyst is added.

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

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

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

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

[0019] In some embodiments of the present application, the reaction temperature of the third reaction is 140-170 DEG C; the temperature of the third aging is 80-140 DEG C, and the time of the third aging is 60-300 min.

[0020] In some embodiments of the present application, the neutralization process is: after the reaction system is cooled to 60-65 DEG C, the acid solution is added dropwise for neutralization.

[0021] In some embodiments of the present application, the acid solution is at least one of formic acid, acetic acid, iso-octanoic acid, and iso-nonyl acid. The addition amount of the acid solution is 0.5-1.5 times of the molar amount of the basic catalyst.

[0022] The present application also provides a low-foaming multi-block polyether.

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

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

[0025] Specifically, the application of the above low-foaming multi-block polyether in preparing a chip cleaning agent.

[0026] The fatty alcohol or isomeric alcohol polyether with 10-18 carbon atoms has good cleaning performance, but the application conditions often limit its application in more industries. The present application controls the proportion of each block by the multi-block method, so that the prepared polyether has a cloud point of 20-30 DEG C, which can meet the ideal working temperature of chip wet cleaning; and the obtained polyether has less small molecule by-products and excellent defoaming performance, which can widen its use conditions and be applied to chip cleaning.

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

[0028] (1) The present application adjusts the block structure to be starter-EO-X-EO, the polyether ends with EO segment, X is PO segment, EO / PO random segment or PO-EO-PO block, and controls the proportion of the tail end EO of the polyether 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 preparation method of the low-foaming multi-block polyether provided by the present application has reasonable process and simple operation, and the prepared product is stable. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 Liquid phase liquid mass contrastive graph of the multi-block polyether prepared for example 1 and comparative example 2. DETAILED DESCRIPTION

[0031] In order to make the skilled in the art more clearly understand the technical solutions described in the present application, the following examples are listed for illustration. It should be pointed out that the following examples do not constitute a limitation on the scope of protection required by the present application.

[0032] The raw materials, reagents or devices used in the following examples, if not specifically stated, can be obtained from conventional commercial channels, or can be obtained by existing known methods.

[0033] Example 1

[0034] A preparation method of a low-foaming multi-block polyether (isomeric decanol multi-block polyether), comprising the following steps:

[0035] 158g isodecanol and 0.57g potassium hydroxide were put into a reaction kettle, and dehydrated under the condition of temperature 85℃ and vacuum-0.098Mpa for 60min; the starter after dehydration was cooled to 50℃, 0.81g DBU was added, and after fully stirring and mixing, nitrogen was placed; then it was raised to the reaction temperature 155℃, and 233g ethylene oxide was added dropwise for reaction; after the dropwise addition of ethylene oxide was completed, the temperature was immediately lowered to 130℃ for curing, and the curing time was 60min; after the curing was completed, it was raised to 155℃, and 293g propylene oxide was added dropwise for reaction; after the dropwise addition of propylene oxide was completed, the temperature was immediately lowered to 130℃ for curing, and the curing time was 180min; after the curing was completed, it was raised to 155℃, and 126g ethylene oxide was added dropwise for reaction; after the dropwise addition of ethylene oxide was completed, the temperature was immediately lowered to 130℃ for curing, and the curing time was 60min. Finally, it was degassed at 100℃ for 20min; after the degassing was completed, it was cooled to 60-65℃, and 0.71g formic acid was added dropwise for neutralization; after the neutralization was completed, the material was discharged at 60℃, and the low-foaming multi-block polyether was prepared.

[0036] Comparative example 1

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

[0038] 158 g of isodecanol and 0.57 g of potassium hydroxide were put into a reaction kettle, and dehydrated at a temperature of 85°C under vacuum-0.098 Mpa for 60 min; after the dehydration was completed, the starting agent was cooled to 50°C, 0.81 g of DBU was added, and after the mixture was fully stirred, nitrogen was introduced; then the temperature was increased to 155°C, and 293 g of propylene oxide was added dropwise for reaction; after the dropwise addition of propylene oxide was completed, the temperature was immediately reduced to 130°C for curing, and the curing time was 180 min; after the curing was completed, the temperature was increased to 155°C, and 359 g of ethylene oxide was added dropwise for reaction; after the dropwise addition of ethylene oxide was completed, the temperature was immediately reduced to 130°C for curing, and the curing time was 60 min; finally, degassing was performed at 100°C for 20 min; after the degassing was completed, the temperature was reduced to 60-65°C, 0.71 g of formic acid was added for neutralization; after the neutralization was completed, the material was discharged at 60°C, and a multi-block polyether was prepared.

[0039] Comparative Example 2

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

[0041] 158 g of isodecanol and 0.57 g of potassium hydroxide were put into a reaction kettle, and dehydrated at a temperature of 85°C under vacuum-0.098 Mpa for 60 min; after the dehydration was completed, the starting agent was cooled to 50°C, 0.81 g of DBU was added, and after the mixture was fully stirred, nitrogen was introduced; then the temperature was increased to 155°C, and 293 g of propylene oxide was added dropwise for reaction; after the dropwise addition of propylene oxide was completed, the temperature was immediately reduced to 130°C for curing, and the curing time was 180 min; after the curing was completed, the temperature was increased to 155°C, and 359 g of ethylene oxide was added dropwise for reaction; after the dropwise addition of ethylene oxide was completed, the temperature was immediately reduced to 130°C for curing, and the curing time was 60 min; finally, degassing was performed at 100°C for 20 min; after the degassing was completed, the temperature was reduced to 60-65°C, 0.71 g of formic acid was added for neutralization; after the neutralization was completed, the material was discharged at 60°C, and a multi-block polyether was prepared.

[0042] Comparative Example 3

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

[0044] Into a reaction kettle, 158 g of isodecyl alcohol and 0.57 g of potassium hydroxide were put, and dehydrated at a temperature of 85°C under vacuum-0.098 Mpa for 60 min; after the dehydration of the starting agent was completed, the temperature was lowered to 50°C, 0.81 g of DBU was added, and after the mixture was fully stirred, nitrogen was introduced; then the temperature was raised to 155°C, and 287 g 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 curing, and the curing time was 60 min; after the curing was completed, the temperature was raised to 155°C, and 293 g 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 curing, and the curing time was 180 min; after the curing was completed, the temperature was raised to 155°C, and 72 g 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 curing, and the curing time was 60 min; finally, degassing was performed at 100°C for 20 min; after the degassing was completed, the temperature was lowered to 60-65°C, 0.71 g of formic acid was added dropwise for neutralization; after the neutralization was completed, the material was discharged at 60°C, and a multi-block polyether was prepared.

[0045] Comparative Example 4

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

[0047] Into a reaction kettle, 158 g of isodecyl alcohol and 0.57 g of potassium hydroxide were put, and dehydrated at a temperature of 85°C under vacuum-0.098 Mpa for 60 min; after the dehydration of the starting agent was completed, the temperature was lowered to 50°C, 0.81 g of DBU was added, and after the mixture was fully stirred, nitrogen was introduced; then the temperature was raised to 155°C, and 287 g 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 curing, and the curing time was 60 min; after the curing was completed, the temperature was raised to 155°C, and 293 g 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 curing, and the curing time was 180 min; after the curing was completed, the temperature was raised to 155°C, and 72 g 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 curing, and the curing time was 60 min; finally, degassing was performed at 100°C for 20 min; after the degassing was completed, the temperature was lowered to 60-65°C, 0.71 g of formic acid was added dropwise for neutralization; after the neutralization was completed, the material was discharged at 60°C, and a multi-block polyether was prepared.

[0048] The multi-block polyethers prepared in Example 1 and Comparative Examples 1-4 were subjected to performance tests, specifically including cloud point (1% water), foaming height, time for foam residue of 8 mL (0.5% water / 25°C), time for foam residue of 5 mL (0.5% water / 25°C). Among them, the foaming performance test was carried out by oscillation method, and each multi-block polyether was configured into a 0.5% aqueous solution, 50 mL of liquid was taken into a cylinder with a stopper, and was oscillated 20 times at 25°C, then placed and observed the foam liquid level, and the time was recorded. The test results are shown in Table 1.

[0049] Table 1

[0050]

[0051] In practical application, the ideal cleaning temperature is 20-30 degrees Celsius, so the cloud point at 20-30°C is the best working temperature, if the cloud point is lower than 20°C, the polyether will precipitate in the cleaning temperature range, and thus lose the cleaning function; if higher than 30°C, the hydrophilicity of the polyether is too strong, which will also affect the cleaning ability.

[0052] As can be seen from Table 1, Example 1 and Comparative Example 1 have the same starter and EO / PO ratio, but due to the difference in block structure, the cloud point of the 1% water solution of the product is greatly different, which also leads to Comparative Example 1 failing to meet the working environment above 12.6°C, and the foaming performance is slightly worse than Example 1. Comparative Examples 3 and 4 are the end EO ratio not in the range of 30%-50%, and their cloud points also cannot meet the requirements.

[0053] The multi-block polyethers prepared in Example 1 and Comparative Example 2 were subjected to liquid chromatography-mass spectrometry analysis, Figure 1 The liquid chromatography-mass spectrometry comparison chart of the multi-block polyethers prepared in Example 1 and Comparative Example 2 is shown in Figure 1. Figure 1 It can be seen that Comparative Example 2 has more small molecule by-products than Example 1, which also leads to the multi-block polyether obtained having high foaming and poor defoaming performance.

[0054] Examples 2-9

[0055] Examples 2-9 provide eight methods for preparing low-foaming multi-block polyethers, and the specific parameters of the starter, dehydration conditions, catalyst used, block structure, reaction temperature, and curing temperature are shown in Table 2:

[0056] Table 2

[0057]

[0058]

[0059] The multi-block polyethers prepared in Examples 2-9 were tested for performance, including cloud point (1% water), foaming height, time for 8 mL of foam to remain (0.5% water / 25°C), and time for 5 mL of foam to remain (0.5% water / 25°C). The results of the testing of Examples 2-9 are shown in Table 3.

[0060] Table 3

[0061]

[0062] As can be seen from Table 3, the multi-block polyethers prepared in Examples 2-9 have a cloud point of 21-30°C, which is the optimal working temperature; the foaming height is less than or equal to 85 mL, 8 mL of foam remains within 4 minutes, and 5 mL of foam remains within 8 minutes and 10 seconds. The foaming is low, and the defoaming performance is excellent. Among them, Examples 7-9 have relatively excellent foaming and defoaming performance because the carbon chain of the selected starter is long enough, without adding an organic base catalyst.

[0063] The above-described examples only express several embodiments of the present application, and the description is more specific and detailed, but it should not be understood as limiting the scope of the patent of the present application. It should be noted that for ordinary skilled in the art, without departing from the concept of the present application, several modifications and improvements can be made, which are all within the scope of protection of the present application. Therefore, the scope of protection of the patent of the present application should be subject to the appended claims.

Claims

1. A method for preparing a low-foaming multi-block polyether, characterized in that, Includes the following steps: The initiator was mixed with an alkaline catalyst, and after heating, the first ethylene oxide was added dropwise for a first reaction and a first ripening. After the first ripening, an epoxide was added for a second reaction and a second ripening. After the second ripening, the second ethylene oxide was added for a third reaction and a third ripening. Finally, after degassing and neutralization, a low-foaming multi-block polyether was obtained. 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 initiator is a fatty alcohol or isomer alcohol having a chain of 10 to 18 carbon atoms; The alkaline catalyst includes a first alkaline catalyst and a second alkaline catalyst. The first alkaline catalyst is selected from at least one of sodium hydroxide, potassium hydroxide, sodium methoxide, and potassium methoxide. The second alkaline catalyst is selected from at least one of tetramethylguanidine, 1,8-diazacyclo[5,4,0]undecene-7, and triethylamine. The amount of the first alkaline catalyst added is 0.05%-1% of the mass of the low-foaming multi-block polyether; the amount of the second alkaline catalyst added is 0.05%-1% of the mass of the low-foaming multi-block polyether. The mixing process of the initiator and the alkaline catalyst is as follows: first, the initiator is mixed with the first alkaline catalyst and dehydrated for 20-180 minutes under conditions of 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.

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 and second ethylene oxides.

3. The preparation method according to claim 1 or 2, characterized in that, The reaction temperature for the first reaction is 140℃-170℃; the reaction temperature for the second reaction is 140℃-170℃; and the reaction temperature for the third reaction is 140℃-170℃.

4. The preparation method according to claim 1 or 2, characterized in that, The temperature for the first maturation is 80-140℃, and the time for the first maturation is 60-300 min; the temperature for the second maturation is 80-140℃, and the time for the second maturation is 60-300 min; the temperature for the third maturation is 80-140℃, and the time for the third maturation is 60-300 min.

5. A low-foaming multi-block polyether, characterized in that, The low-foaming multi-block polyether is prepared by any one of claims 1-4, and the structure of the polyether is initiator-EO-X-EO, wherein X is a PO segment, an EO / PO random segment, or a PO-EO-PO block.

6. The application of the low-foaming multi-block polyether according to claim 5 in the preparation of chip cleaning agents.

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