A low-foaming nonionic Gemini surfactant and its preparation method

Abstract

This invention discloses a low-foaming nonionic Gemini surfactant and its preparation method, comprising the following steps: dissolving di-tert-amylhydroquinone in acetonitrile and adding it to a reaction vessel; adding a catalyst to the reaction vessel and replacing the air in the reaction vessel with an inert gas; heating the reaction vessel and then introducing ethylene oxide to carry out the reaction; after the reaction, cooling the temperature of the reaction vessel to room temperature and collecting the crude purple-red liquid product; rotary evaporating the obtained crude purple-red liquid product, then extracting it with dichloromethane or ethyl acetate, followed by rotary evaporation again, and drying to obtain the low-foaming nonionic Gemini surfactant. This invention provides a low-foaming nonionic Gemini surfactant, which, as a surfactant additive for wet electronic chemicals in the semiconductor and novel display fields, can effectively reduce the contact angle of wet electronic chemicals, enhance their wettability, and simultaneously reduce foaming during use.

Description

Technical Field

[0001] This invention relates to the field of surfactant technology, and in particular to a low-foaming nonionic Gemini surfactant and its preparation method. Background Technology

[0002] Surfactants are substances that significantly reduce the surface tension of a target solution. Based on the different hydrophilic head groups, they are classified into four types: nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Surfactants generally possess good emulsifying, wetting, foaming, or defoaming properties, and can also achieve dispersion, flocculation, antistatic, and bactericidal effects, thus being widely used in textiles, pharmaceuticals, and chemicals. Nonionic surfactants, in particular, have advantages such as not ionizing in aqueous solutions, high stability, and susceptibility to the effects of inorganic salts and acids / bases. They lack electrostatic repulsion during foam formation and stabilization, making it less prone to foam stability, thus exhibiting better low-foaming properties. The unique structure of Gemini surfactants gives them, compared to traditional surfactants, higher surface (interfacial) activity, lower critical micelle concentration, better solubilizing and wetting properties, and stronger emulsifying and antibacterial capabilities.

[0003] Wet electronic materials used in the semiconductor and new display fields mainly include etching solutions, stripping solutions, and cleaning solutions, generally used in etching and wafer surface cleaning processes during integrated circuit and display panel manufacturing. With the continuous refinement of integrated circuits and display panels and the shrinking of process dimensions, the wettability requirements of wet electronic chemicals are constantly increasing, demanding that the wet electronic chemical system possess low surface tension. On the other hand, since many wet electronic chemicals are applied using a spray method, foam is generated when the chemicals are sprayed onto the wafer or panel surface. The presence of foam can affect the contact between the wet electronic chemicals and the surface material being treated, resulting in defects.

[0004] Low-foaming nonionic Gemini surfactants are suitable for wet electronic chemicals in the semiconductor and new display fields. They effectively improve the wetting properties of wet electronic chemicals even with small amounts added, while their low foaming rate promotes uniform and thorough contact between the wet electronic chemicals and the surface to be treated, thereby reducing defects generated during the manufacturing process of semiconductor display panels. Furthermore, these surfactants do not introduce additional metal ions and possess excellent resistance to strong alkalis and acids. Summary of the Invention

[0005] The purpose of this invention is to provide a low-foaming nonionic Gemini surfactant and its preparation method, so as to overcome the shortcomings of the prior art.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] This application discloses a method for preparing a low-foaming nonionic Gemini surfactant, which specifically includes the following steps:

[0008] S1. Dissolve di-tert-pentylhydroquinone in acetonitrile and add it to the reaction vessel; the mass ratio of di-tert-pentylhydroquinone to acetonitrile is 1:5-8;

[0009] S2. Add a catalyst to the reaction vessel and replace the air in the reaction vessel with an inert gas;

[0010] S3. Heat the reaction vessel to 65-85°C, and then introduce ethylene oxide to carry out the reaction;

[0011] S4. After reacting for 42-52 hours, the temperature of the reaction vessel was lowered to 15-25°C, and the crude product of purple-red liquid was collected.

[0012] S5. The crude purple-red liquid obtained in step S4 is subjected to rotary evaporation, then extracted with dichloromethane or ethyl acetate, and then subjected to rotary evaporation again. After drying, the target product, a reddish-purple oily liquid, is obtained, which is a low-foaming nonionic Gemini surfactant.

[0013] Preferably, the catalyst used in step S2 is triethylamine and potassium hydroxide.

[0014] Preferably, the molar ratio of di-tert-pentylhydroquinone to triethylamine is 10:1 to 16:1.

[0015] Preferably, the molar ratio of the di-tert-pentylhydroquinone to potassium hydroxide is 32:1 to 34:1.

[0016] Preferably, the molar ratio of the di-tert-pentylhydroquinone to ethylene oxide is 1:12 to 1:20.

[0017] Preferably, the low-foaming nonionic Gemini surfactant has the following structural formula:

[0018]

[0019] Where n is a natural number.

[0020] Preferably, n is 6 to 8.

[0021] This invention also discloses a low-foaming nonionic Gemini surfactant, the structural formula of which is as follows:

[0022]

[0023] Where n is a natural number; it is prepared using the above-described method for preparing a low-foaming nonionic Gemini surfactant.

[0024] Preferably, n is 6 to 8.

[0025] Preferably, n is 6 or 7.

[0026] The beneficial effects of this invention are:

[0027] 1. The product of this invention is a low-foaming nonionic Gemini surfactant, which can be used as a surfactant additive for wet electronic chemicals in the semiconductor and new display fields. After being added, it can effectively reduce the contact angle of wet electronic chemicals, enhance their wettability, and reduce foaming during use.

[0028] 2. The low-foaming nonionic Gemini surfactant of this invention does not ionize in solution and does not introduce additional impurity ions;

[0029] 3. The present invention provides a low-foaming nonionic Gemini surfactant with a moderately long polyoxyethylene ether chain, which avoids the problem of poor solubility in aqueous solutions due to excessively short polyoxyethylene ether chains; at the same time, the molecular weight is small, which avoids the formation of particulate impurities after addition.

[0030] 4. The low-foaming nonionic Gemini surfactant of this invention lacks electrostatic repulsion during the formation and stabilization of foam, making it difficult for foam to remain stable. Therefore, it has better low-foaming properties. Wet electronic chemicals can make uniform and sufficient contact with the surface to be treated, which is beneficial to reducing defects in the semiconductor display panel manufacturing process.

[0031] 5. The special structure of the low-foaming nonionic Gemini surfactant of this invention makes it easy to be adsorbed on gas / liquid surfaces, with good wettability enhancement, and has excellent properties such as resistance to strong alkali and strong acid environments. It can be used in conjunction with a variety of wet electronic chemicals such as developing solutions and etching solutions in the semiconductor and new display fields.

[0032] 6. The low-foaming nonionic Gemini surfactant of this invention is fluorine-free, non-toxic, biodegradable, and environmentally friendly.

[0033] 7. The method for preparing a low-foaming nonionic Gemini surfactant of the present invention is simple, practical, and does not require high temperature and has low energy consumption.

[0034] The features and advantages of the present invention will be described in detail through embodiments and in conjunction with the accompanying drawings. Attached Figure Description

[0035] Figure 1This is the infrared spectrum of a low-foaming nonionic Gemini surfactant (n=6) from Example 1;

[0036] Figure 2 This is Example 1, a low-foaming nonionic Gemini surfactant (n=6). 1 HNMR spectrum;

[0037] Figure 3 This is a contact angle diagram before and after adding a low-foaming nonionic Gemini surfactant (n=6) to the developer;

[0038] Figure 4 This is the infrared spectrum of a low-foaming nonionic Gemini surfactant (n=7) from Example 2;

[0039] Figure 5 This is Example 2, a low-foaming nonionic Gemini surfactant (n=7). 1 HNMR spectrum;

[0040] Figure 6 This is a contact angle diagram before and after adding a low-foaming nonionic Gemini surfactant (n=7) to the developer;

[0041] Figure 7 This is the infrared spectrum of a low-foaming nonionic Gemini surfactant (n=8) from Example 3;

[0042] Figure 8 This is Example 3, a low-foaming nonionic Gemini surfactant (n=8). 1 HNMR spectrum;

[0043] Figure 9 This is a contact angle diagram before and after adding a low-foaming nonionic Gemini surfactant (n=8) to the developer. Detailed Implementation

[0044] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. However, it should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of the invention. Furthermore, descriptions of well-known structures and technologies are omitted in the following description to avoid unnecessarily obscuring the concept of the invention.

[0045] This invention provides a method for preparing a low-foaming nonionic Gemini surfactant, specifically including the following steps:

[0046] S1. Dissolve di-tert-pentylhydroquinone in acetonitrile and add it to the reaction vessel; the mass ratio of di-tert-pentylhydroquinone to acetonitrile is 1:5-8;

[0047] S2. Add a catalyst to the reaction vessel and replace the air in the reaction vessel with an inert gas;

[0048] S3. Heat the reaction vessel to 65-85°C, and then introduce ethylene oxide to carry out the reaction;

[0049] S4. After reacting for 42-52 hours, the temperature of the reaction vessel was lowered to 15-25°C, and the crude product of purple-red liquid was collected.

[0050] S5. The crude purple-red liquid obtained in step S4 is subjected to rotary evaporation, then extracted with dichloromethane or ethyl acetate, and then subjected to rotary evaporation again. After drying, the target product, a reddish-purple oily liquid, is obtained, which is a low-foaming nonionic Gemini surfactant.

[0051] In one feasible embodiment, the catalyst in step S2 is triethylamine and potassium hydroxide; the molar ratio of di-tert-pentylhydroquinone to triethylamine is 10:1 to 16:1. The molar ratio of di-tert-pentylhydroquinone to potassium hydroxide is 32:1 to 34:1.

[0052] In one feasible embodiment, the molar ratio of the di-tert-pentylhydroquinone to ethylene oxide is 1:12 to 1:20.

[0053] The structural formula of the low-foaming nonionic Gemini surfactant is as follows:

[0054]

[0055] Where n is a natural number.

[0056] In one feasible embodiment, n is 6 to 8.

[0057] Example 1:

[0058] The preparation method of this invention is shown in the figure below:

[0059]

[0060] The reactants are di-tert-pentylhydroquinone and ethylene oxide; Et3N is triethylamine, KOH is potassium hydroxide, and ACN is acetonitrile.

[0061] First, 100g of di-tert-pentylhydroquinone was dissolved in 500g of acetonitrile, and then added to a 5L high-pressure reactor. Triethylamine (molar ratio of di-tert-pentylhydroquinone to triethylamine was 16:1) and potassium hydroxide (molar ratio of di-tert-pentylhydroquinone to potassium hydroxide was 33:1) were added to the reactor as catalysts. After purging the reactor with nitrogen, the temperature was raised to 85℃ and ethylene oxide (molar ratio of di-tert-pentylhydroquinone to ethylene oxide was 1:12) was slowly introduced. After reacting for 48h, the temperature was lowered to 15℃ and the crude product, a purplish-red liquid, was collected. The crude product was then rotary evaporated, extracted with dichloromethane, and rotary evaporated again. Finally, it was dried in a vacuum drying oven to obtain the target product, a reddish-purple oily liquid.

[0062] like Figure 1 As shown, the infrared spectrum of this embodiment is as follows:

[0063] 3435cm -1 (peak 1) is the absorption peak of the stretching vibration of the hydroxyl group; 3000-2870 cm⁻¹ -1 (peak 2) is the absorption peak of the stretching vibration of aliphatic CH; 1613 cm⁻¹ -1 (peak3), 1504cm -1 (peak4) and 1459cm -1 Peak 5 is the absorption peak due to the vibration of the benzene ring skeleton; 1380 cm⁻¹ -1 Peak 6 is the absorption peak of the bending vibration of methyl groups; 1209 cm⁻¹ -1 (peak 7) is the absorption peak of the CO stretching vibration formed by carbon and oxygen on the benzene ring; 1150-1060 cm⁻¹ -1 (peak8) is the stretching vibration absorption peak of aliphatic ethers.

[0064] like Figure 2 As shown in this embodiment 1 HNMR spectrum;

[0065] 1 HNMR (400MHz, CDCl3) δ6.76 (d, J=28.1Hz, 1H), 4.20–3.47 (m, 23H), 1.81 (dd, J=14.3, 7.0Hz, 2H), 1.46–1.18 (m, 6H), 0.62 (t, J=7.2Hz, 3H).

[0066] like Figure 3 As shown in the figure, the contact angle diagrams of the low-foaming nonionic Gemini surfactant before and after the addition of the low-foaming nonionic Gemini surfactant to the developer are as follows: It can be seen from the comparison of the figures that the contact angle of the interface becomes smaller after the addition of the low-foaming nonionic Gemini surfactant to the developer, indicating that the wettability of the developer is enhanced.

[0067] Example 2:

[0068] 200g of di-tert-pentylhydroquinone was dissolved in 1200g of acetonitrile and then added to a 10L high-pressure reactor. Triethylamine (molar ratio of di-tert-pentylhydroquinone to triethylamine was 12:1) and potassium hydroxide (molar ratio of di-tert-pentylhydroquinone to potassium hydroxide was 34:1) were added to the reactor as catalysts. After purging the reactor with nitrogen, the temperature was raised to 75℃ and ethylene oxide (molar ratio of di-tert-pentylhydroquinone to ethylene oxide was 1:16) was slowly introduced. After reacting for 52 hours, the temperature was lowered to 25℃ and the crude product, a purplish-red liquid, was collected. The crude product was then rotary evaporated, extracted with dichloromethane, and rotary evaporated again. Finally, it was dried in a vacuum drying oven to obtain the target product, a reddish-purple oily liquid.

[0069] like Figure 4 As shown, the infrared spectrum of this embodiment is as follows:

[0070] 3448cm -1 (peak 1) is the absorption peak of the stretching vibration of the hydroxyl group; 3000-2870 cm⁻¹ -1 (peak 2) is the absorption peak of the stretching vibration of aliphatic CH; 1613 cm⁻¹ -1 (peak3), 1504cm -1 (peak4) and 1459cm -1 Peak 5 is the absorption peak due to the vibration of the benzene ring skeleton; 1380 cm⁻¹ -1 Peak 6 is the absorption peak of the bending vibration of methyl groups; 1209 cm⁻¹ -1 (peak 7) is the absorption peak of the CO stretching vibration formed by carbon and oxygen on the benzene ring; 1150-1060 cm⁻¹ -1 (peak8) is the stretching vibration absorption peak of aliphatic ethers.

[0071] like Figure 5 As shown in this embodiment 1 HNMR spectrum;

[0072] 1 HNMR (400MHz, CDCl3) δ6.76 (d, J=28.1Hz, 1H), 4.28–3.47 (m, 28H), 1.89–1.70 (m, 2H), 1.34 (d, J=20.4Hz, 6H), 0.74–0.54 (m, 3H).

[0073] like Figure 6As shown in the figure, the contact angle diagrams of the low-foaming nonionic Gemini surfactant before and after the addition of the low-foaming nonionic Gemini surfactant to the developer are as follows: It can be seen from the comparison of the figures that the contact angle of the interface becomes smaller after the addition of the low-foaming nonionic Gemini surfactant to the developer, indicating that the wettability of the developer is enhanced.

[0074] Example 3:

[0075] 100g of di-tert-pentylhydroquinone was dissolved in 800g of acetonitrile and then added to a 5L high-pressure reactor. Triethylamine (molar ratio of di-tert-pentylhydroquinone to triethylamine was 10:1) and potassium hydroxide (molar ratio of di-tert-pentylhydroquinone to potassium hydroxide was 32:1) were added to the reactor as catalysts. After purging the reactor with nitrogen, the temperature was raised to 65℃ and ethylene oxide (molar ratio of di-tert-pentylhydroquinone to ethylene oxide was 1:20) was slowly introduced. After reacting for 42h, the temperature was lowered to 20℃ and the crude product, a purplish-red liquid, was collected. The crude product was then rotary evaporated, extracted with ethyl acetate, and rotary evaporated again. Finally, it was dried in a vacuum drying oven to obtain the target product, a reddish-purple oily liquid.

[0076] like Figure 7 As shown, the infrared spectrum of this embodiment is as follows:

[0077] 3435cm -1 (peak 1) is the absorption peak of the stretching vibration of the hydroxyl group; 3000-2870 cm⁻¹ -1 (peak 2) is the absorption peak of the stretching vibration of aliphatic CH; 1613 cm⁻¹ -1 (peak3), 1504cm -1 (peak4) and 1459cm -1 Peak 5 is the absorption peak due to the vibration of the benzene ring skeleton; 1380 cm⁻¹ -1 Peak 6 is the absorption peak of the bending vibration of methyl groups; 1209 cm⁻¹ -1 (peak 7) is the absorption peak of the CO stretching vibration formed by carbon and oxygen on the benzene ring; 1150-1060 cm⁻¹ -1 (peak8) is the stretching vibration absorption peak of aliphatic ethers.

[0078] like Figure 8 As shown in this embodiment 1 HNMR spectrum;

[0079] 1 HNMR (400MHz, CDCl3) δ6.76 (d, J=28.0Hz, 1H), 4.23–3.50 (m, 31H), 1.92–1.73 (m, 2H), 1.34 (d, J=20.4Hz, 6H), 0.81–0.49 (m, 3H);

[0080] like Figure 9 As shown in the figure, the contact angle diagrams of the low-foaming nonionic Gemini surfactant before and after the addition of the surfactant to the developer in this embodiment are shown. The comparison of the figures shows that the contact angle of the interface becomes smaller after the addition of the low-foaming nonionic Gemini surfactant to the developer, indicating that the wettability of the developer is enhanced.

[0081] Foaming ability test: The foaming ability of the surfactant solution is measured by the initial foaming volume; prepare a surfactant solution with a concentration of 0.001 mol / L, add 5 mL of surfactant solution to a stoppered graduated cylinder with a specification of 25 mL, and generate foam by vigorously shaking the graduated cylinder up and down 20 times, and immediately record the volume of foam generated (mL).

[0082] Table 1 shows the foaming properties test results of low-foaming nonionic Gemini surfactants:

[0083] Table 1

[0084] 1 6 0.1 2 7 0.5 3 8 0.7

[0085] The data in the table shows that the initial foaming volume of this low-foaming nonionic Gemini surfactant solution is small, and its foaming ability is low.

[0086] Table 2 shows the contact angle and surface tension data before and after adding a low-foaming nonionic Gemini surfactant (concentration of 0.001 mol / L) to a semiconductor display wet electronic chemical (taking the developer as an example).

[0087] Table 2

[0088]

[0089]

[0090] The data in the table show that the contact angle and surface tension of the developer solution decreased significantly after the addition of the low-foaming nonionic Gemini surfactant.

[0091] Table 3 shows the evaluation of development results before and after adding a low-foaming nonionic Gemini surfactant (concentration of 0.001 mol / L) to the semiconductor display wet electronic chemicals (taking the developer as an example);

[0092] Table 3

[0093]

[0094] Evaluation criteria for development results: A indicates uniform development, B indicates uneven development in some areas, and C indicates uneven development. As can be seen from the data in the table, the development results are significantly improved after adding the low-foaming nonionic Gemini surfactant to the developer.

[0095] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions or improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a low-foaming nonionic Gemini surfactant, characterized in that, Specifically, the steps include the following: S1. Dissolve di-tert-pentylhydroquinone in acetonitrile and add it to the reaction vessel; the mass ratio of di-tert-pentylhydroquinone to acetonitrile is 1:5~8; S2. Add a catalyst to the reaction vessel and replace the air in the reaction vessel with an inert gas; S3. Heat the reaction vessel to 65~85℃, and then introduce ethylene oxide to carry out the reaction; S4. After reacting for 42-52 hours, the temperature of the reaction vessel was lowered to 15-25℃, and the crude product in a purplish-red liquid was collected. S5. The crude purple-red liquid obtained in step S4 is subjected to rotary evaporation, then extracted with dichloromethane or ethyl acetate, and then subjected to rotary evaporation again. After drying, the target product, a reddish-purple oily liquid, is obtained, which is a low-foaming nonionic Gemini surfactant. The structural formula of the low-foaming nonionic Gemini surfactant is as follows: ， Where n is 6 to 8.

2. The method for preparing a low-foaming nonionic Gemini surfactant as described in claim 1, characterized in that: In step S2, the catalyst used is triethylamine and potassium hydroxide.

3. The method for preparing a low-foaming nonionic Gemini surfactant as described in claim 2, characterized in that: The molar ratio of di-tert-pentylhydroquinone to triethylamine is 10:1 to 16:

1.

4. The method for preparing a low-foaming nonionic Gemini surfactant as described in claim 2, characterized in that: The molar ratio of di-tert-pentylhydroquinone to potassium hydroxide is 32:1 to 34:

1.

5. The method for preparing a low-foaming nonionic Gemini surfactant as described in claim 1, characterized in that: The molar ratio of di-tert-pentylhydroquinone to ethylene oxide is 1:12 to 1:

20.

6. A low-foaming nonionic Gemini surfactant, characterized in that: The structural formula of the low-foaming nonionic Gemini surfactant is as follows: ， Where n is 6 to 8; it is prepared by the method for preparing a low-foaming nonionic Gemini surfactant as described in any one of claims 1 to 5.

7. The low-foaming nonionic Gemini surfactant as described in claim 6, characterized in that: The value of n is 6 or 7.

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