A nonionic Gemini surfactant and its preparation method and application

Abstract

The present invention discloses a nonionic Gemini surfactant and a preparation method and application thereof. The structural formula of the surfactant is as follows: wherein n is a natural number. The present invention can prepare the nonionic Gemini surfactant under normal pressure without high temperature. The nonionic Gemini surfactant is a surfactant suitable for wet electronic chemicals in the semiconductor and new display fields, and can efficiently improve the wettability of wet electronic chemicals when the addition amount is small.

Description

Technical Field

[0001] The invention belongs to the technical field of surfactants, and specifically relates to a nonionic Gemini surfactant and a preparation method and application thereof. Background Art

[0002] Surfactant is a substance that can significantly reduce the surface tension of the target solution. It is divided into four types according to the hydrophilic head group: anionic surfactants, cationic surfactants, zwitterionic surfactants and non-ionic surfactants. Surfactants generally have good emulsification, wetting, foaming or defoaming properties, and can also achieve dispersion, flocculation, antistatic and sterilization effects. They are widely used in textiles, pharmaceuticals, cosmetics, food, shipbuilding, civil engineering, mining and other fields. Gemini surfactants are a class of substances containing two hydrophilic groups and two hydrophobic tail chains, and the hydrophilic groups are connected by chemical bonds. Compared with traditional single-chain surfactants, the double hydrophilic and double hydrophobic molecular structure has a lower critical micelle concentration and a higher ability to reduce the surface tension of the target solution.

[0003] Wet electronic materials used in semiconductor and new display fields mainly include etching solutions, stripping solutions, developers and cleaning solutions, etc., which are generally used in etching, wafer surface cleaning and other processes in the manufacturing process of integrated circuits and display panels. With the continuous refinement of integrated circuits and display panels, the process size continues to shrink, and the wettability requirements of wet electronic chemicals continue to increase, which requires the wet electronic chemical system to have low surface tension and higher wettability.

[0004] Chinese patent CN112195021A discloses a Gemini polyoxyethylene ether succinate surfactant for oil displacement and its preparation method, wherein the surfactant is Gemini alkylphenol polyoxyethylene sulfosuccinate. The invention is prepared by mixing alkylphenol polyoxyethylene ether and paraformaldehyde, vacuumizing to -0.06Mpa to -0.08Mpa, filling with nitrogen, heating to 100℃ to 120℃, stirring for 2h under the condition of 0.05 to 0.5Mpa; cooling to 70℃ to 100℃, adding maleic anhydride, reacting for 4 to 6h, neutralizing with alkaline solution to pH of product solution = 7; adding a solvent containing a catalyst and a sulfonating agent, setting the speed to 350r / min, stirring for 8 to 10h under the condition of setting the heating temperature to 70℃ to 100℃, and obtaining Gemini polyoxyethylene ether succinate surfactant for oil displacement, and obtaining Gemini alkylphenol polyoxyethylene ether sulfosuccinate that is salt-resistant and temperature-resistant and has high wettability, which is particularly suitable for high-temperature and high-salt oil reservoirs. The invention provides a Gemini alkylphenol polyoxyethylene ether sulfosuccinate type temperature-resistant and salt-resistant ultra-low interfacial tension surfactant, which has a good prospect for promotion and application and good social and economic benefits. However, the synthesis conditions involved in the invention are low pressure and high temperature, and the reaction conditions are relatively harsh. At the same time, the obtained surfactant is mainly used in oil recovery technology. Whether it can be used in wet electronic chemicals cannot be known from its specification. Summary of the invention

[0005] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a non-ionic Gemini surfactant and a preparation method and application thereof. The present invention can prepare the non-ionic Gemini surfactant under normal pressure conditions without high temperature. The non-ionic Gemini surfactant is a surfactant suitable for wet electronic chemicals in the semiconductor and new display fields, and can efficiently improve the wettability of wet electronic chemicals when added in a small amount.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] A nonionic Gemini surfactant, the structural formula of the surfactant is as follows:

[0008]

[0009] Wherein, n is a natural number.

[0010] Preferably, n is an integer of 4-11.

[0011] More preferably, n can be 4, 5, 6, 7, 8, 9, 10, or 11.

[0012] The present invention also protects a method for preparing the nonionic Gemini surfactant as described above, comprising the following steps:

[0013] S1, adding polyethylene glycol monomethyl ether and p-toluenesulfonyl chloride into a reaction container, then adding a reaction solvent and a catalyst, stirring to react, extracting after the reaction is completed, and rotary evaporation drying to obtain a sulfonate;

[0014] S2, adding the sulfonate prepared in step S1 into N,N-dimethylformamide, and stirring to obtain a sulfonate solution;

[0015] S3, adding di-tert-amyl hydroquinone and sodium hydride into a reaction vessel, introducing an inert gas to expel the air, then adding a solvent and stirring evenly, then adding the sulfonate solution in step S2 into the reaction vessel, heating to react, cooling after the reaction is completed, obtaining an orange-red liquid, and then extracting to obtain a crude product;

[0016] S4. The crude product in step S3 is subjected to column chromatography to obtain a nonionic Gemini surfactant.

[0017] Preferably, in step S1, the reaction solvent is dichloromethane, and the catalyst is triethylamine.

[0018] In the present invention, the reaction solvent in step S1 may also be N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, etc.

[0019] Preferably, the molecular weight of the polyethylene glycol monomethyl ether in step S1 is 200-500; the molar ratio of the polyethylene glycol monomethyl ether to p-toluenesulfonyl chloride is 1:1-1.5; and the molar ratio of the polyethylene glycol monomethyl ether to triethylamine is 1:1.8-2.2.

[0020] More preferably, the molecular weight of the polyethylene glycol monomethyl ether in step S1 can be 200, 250, 300, 350, 400, 450, or 500; the molar ratio of the polyethylene glycol monomethyl ether to p-toluenesulfonyl chloride is 1:1-1.5, and can be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, or 1:1.5; the molar ratio of the polyethylene glycol monomethyl ether to triethylamine is 1:1.8-2.2, and can be 1:1.8, 1:1.85, 1:1.9, 1:1.95, 1:2, 1:2.05, 1:2.1, 1:2.15, or 1:2.2.

[0021] Preferably, the stirring reaction in step S1 is carried out at room temperature and normal pressure for 30-40 hours.

[0022] More preferably, the room temperature in step S1 is 10-30°C, and can be 10°C, 12°C, 14°C, 15°C, 17°C, 19°C, 20°C, 22°C, 24°C, 25°C, 27°C, 29°C, 30°C, and the reaction time can be 30h, 31h, 32h, 33h, 34h, 35h, 36h, 37h, 38h, 39h, 40h.

[0023] Preferably, the molar ratio of di-tert-amylhydroquinone to sodium hydride in step S3 is 1:2.5-3.5.

[0024] More preferably, the molar ratio of di-tert-amylhydroquinone to sodium hydride in step S3 can be 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3.0, 1:3.1, 1:3.2, 1:3.3, 1:3.4, or 1:3.5.

[0025] Preferably, the molar ratio of di-tert-amylhydroquinone to sulfonate in step S3 is 1:2-3.

[0026] More preferably, the molar ratio of di-tert-amylhydroquinone to sulfonate in step S3 is 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, or 1:3.

[0027] Preferably, the solvent in step S3 is N,N-dimethylformamide; the heating reaction is carried out at normal pressure and 65-85° C. for 30-40 hours.

[0028] More preferably, the reaction temperature in step S3 can be 65°C, 67°C, 69°C, 70°C, 72°C, 74°C, 75°C, 77°C, 79°C, 80°C, 82°C, 84°C, 85°C; the reaction time can be 30h, 31h, 32h, 33h, 34h, 35h, 36h, 37h, 38h, 39h, 40h.

[0029] The present invention also protects the use of the nonionic Gemini surfactant as described above in wet electronic chemicals, wherein the wet electronic chemicals are etching solutions, stripping solutions, developing solutions or cleaning solutions.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] (1) The nonionic Gemini surfactant provided by the present invention is 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 and enhance their wettability. At the same time, the nonionic Gemini surfactant does not ionize in the solution and does not introduce additional impurity ions. The nonionic Gemini surfactant structure does not contain fluorine, is non-toxic and biodegradable, and is environmentally friendly. In addition, the special structure of the surfactant makes it easy to adsorb on the gas / liquid surface, has a good wettability enhancement effect, and has excellent properties such as resistance to strong alkaline and strong acid environments. It can be simultaneously adapted to a variety of wet electronic chemicals such as developers and etching solutions in the semiconductor and new display fields.

[0032] (2) The preparation method of the nonionic Gemini surfactant provided by the present invention has the following preparation conditions: normal pressure conditions, low reaction temperature, no need for high temperature, and is safer; the preparation method is simple and highly practical.

[0033] (3) The nonionic Gemini surfactant provided by the present invention can significantly reduce the surface tension of the developer when applied to the developer, increase the wettability of the developer and the photoresist, and reduce the collapse of the photoresist during the development process. It can be used to form ultra-fine photolithography patterns less than 130nm, thereby improving the application performance of the product. Moreover, the surfactant will not introduce additional metal ions and has excellent properties such as resistance to strong alkaline and strong acid environments. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 is an infrared spectrum of the nonionic Gemini surfactant (n=4) prepared in Example 1 of the present invention;

[0035] Figure 2 is the 1HNMR spectrum of the nonionic Gemini surfactant (n=4) prepared in Example 1 of the present invention;

[0036] Figure 3 is a contact angle diagram before and after the nonionic Gemini surfactant (n=4) prepared in Example 1 of the present invention is added to the developer;

[0037] Figure 4 is the infrared spectrum of the nonionic Gemini surfactant (n=7) prepared in Example 2 of the present invention;

[0038] Figure 5 is the 1HNMR spectrum of the nonionic Gemini surfactant (n=7) prepared in Example 2 of the present invention;

[0039] Figure 6 is a contact angle diagram before and after the nonionic Gemini surfactant (n=7) prepared in Example 1 of the present invention is added to the developer;

[0040] Figure 7 is an infrared spectrum of the nonionic Gemini surfactant (n=11) prepared in Example 1 of the present invention;

[0041] Figure 8 is the 1HNMR spectrum of the nonionic Gemini surfactant (n=11) prepared in Example 1 of the present invention;

[0042] Fig. 9 Graphs showing contact angles before and after the nonionic Gemini surfactant (n=11) prepared in Example 3 of the present invention is added to the developer. DETAILED DESCRIPTION

[0043] 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.

[0044] The embodiment of the present invention provides a nonionic Gemini surfactant prepared under normal pressure conditions, which specifically includes the following steps:

[0045] S1, adding polyethylene glycol monomethyl ether and p-toluenesulfonyl chloride into a reaction vessel, then adding a reaction solvent and a catalyst, reacting at room temperature and normal pressure for 30-40 hours, collecting a yellow liquid, i.e., a crude sulfonate; then extracting the crude sulfonate with dichloromethane, and drying it by rotary evaporation to obtain a sulfonate;

[0046] S2, adding the sulfonate prepared in step S1 into N,N-dimethylformamide, and stirring to obtain a sulfonate solution;

[0047] S3, adding di-tert-amylhydroquinone and sodium hydride into a reaction container, replacing the air in the reaction container with an inert gas, then adding N,N-dimethylformamide as a solvent, and stirring at room temperature for 20-40 minutes at normal pressure, then injecting the sulfonate solution in step S2 into the reaction container with a needle, heating to 65-85° C. at normal pressure and reacting for 30-40 hours, cooling to 15-25° C. after the reaction is completed, collecting the orange-red liquid, extracting with ethyl acetate, and rotary drying to obtain a crude product;

[0048] S4. The crude product in step S3 is subjected to column chromatography, wherein the stationary phase of the column chromatography is silica gel powder and the mobile phase is a mixture of dichloromethane and methanol, to obtain a target product, a yellow-red oily liquid, i.e., a nonionic Gemini surfactant.

[0049] In some embodiments, the reaction solvent in step S1 is dichloromethane, the catalyst is triethylamine; the molecular weight of the polyethylene glycol monomethyl ether is 200-500; the molar ratio of the polyethylene glycol monomethyl ether to p-toluenesulfonyl chloride is 1:1-1.5; the molar ratio of the polyethylene glycol monomethyl ether to triethylamine is 1:1.8-2.2; the molar ratio of di-tert-amyl hydroquinone to sodium hydride is 1:2.5-3.5; the molar ratio of di-tert-amyl hydroquinone to sulfonate is 1:2-3.

[0050] The structural formula of the nonionic Gemini surfactant prepared under normal pressure conditions is as follows:

[0051]

[0052] Where n is a natural number;

[0053] In some embodiments, n is 4 to 11, and can be 4, 5, 6, 7, 8, 9, 10, or 11.

[0054] In the present invention, the reaction route for preparing the nonionic Gemini surfactant is as follows:

[0055]

[0056] The above reactants are p-toluenesulfonyl chloride and polyethylene glycol monomethyl ether in sequence, the product is sulfonate, Et3N is triethylamine, and DCM is dichloromethane.

[0057]

[0058] The reactants are di-tert-amyl hydroquinone and sulfonate in sequence, the product is a non-ionic Gemini surfactant, NaH is sodium hydride, and DMF is N,N-dimethylformamide.

[0059] Example 1

[0060] A method for preparing a nonionic Gemini surfactant under normal pressure comprises the following steps:

[0061] S1, adding 20g of polyethylene glycol monomethyl ether with a molecular weight of 200 and p-toluenesulfonyl chloride into a reaction container, the molar ratio of polyethylene glycol monomethyl ether to p-toluenesulfonyl chloride being 1:1, putting into a rotor and adding dichloromethane, stirring evenly, adding triethylamine, the molar ratio of polyethylene glycol monomethyl ether to triethylamine being 1:2, reacting at room temperature and normal pressure for 30h, collecting a yellow liquid, i.e., a crude sulfonate; then extracting the crude sulfonate with dichloromethane, the extraction time being 10min, and obtaining a sulfonate after rotary evaporation and drying;

[0062] S2, adding the sulfonate prepared in step S1 into N,N-dimethylformamide, and stirring to obtain a sulfonate solution;

[0063] S3, adding 2g of di-tert-amyl hydroquinone and sodium hydride into a reaction container, the molar ratio of di-tert-amyl hydroquinone to sodium hydride is 1:2.5, replacing the air in the reaction container with an inert gas, placing a rotor and adding N,N-dimethylformamide as a solvent, and stirring at room temperature and normal pressure for 20 minutes, then injecting the sulfonate solution in step S2 into the reaction container with a needle, the molar ratio of di-tert-amyl hydroquinone to sulfonate is 1:2, heating to 75°C under normal pressure and reacting for 36 hours, cooling to 20°C after the reaction is completed, collecting the orange-red liquid, extracting with ethyl acetate, the extraction time is 10 minutes, and rotary evaporation to obtain a crude product;

[0064] S4. The crude product in step S3 is subjected to column chromatography, wherein the stationary phase of the column chromatography is silica gel powder and the mobile phase is a mixture of dichloromethane and methanol, to obtain a target product, a yellow-red oily liquid, i.e., a nonionic Gemini surfactant.

[0065] like Figure 1 As shown, the infrared spectrum of the nonionic Gemini surfactant of this embodiment:

[0066] 3000-2870cm -1 (peak1) is the stretching vibration absorption peak of aliphatic CH; 1505cm -1 (peak2), 1458cm -1 (peak3) is the absorption peak of benzene ring skeleton vibration; 1380cm -1 (peak4) There are two peaks, which are the bending vibration absorption peaks of methyl; 1207cm -1 (peak5) is the stretching vibration absorption peak of CO in phenol; 1150-1060cm -1 (peak6) is the stretching vibration absorption peak of fatty ethers.

[0067] like Figure 2 As shown, the nonionic Gemini surfactant of this embodiment 1 HNMR spectrum:

[0068] 1 HNMR (400MHz, CDCl3) δ6.72 (s, 1H), 4.09 (t, J = 4.7Hz, 2H), 3.97–3.30 (m, 19H), 1.90–1.71 (m, 2H), 1.33 (d, J = 19.9Hz, 7H), 0.62 (t, J = 7.3Hz, 3H).

[0069] like Figure 3As shown in FIG. 1 , the contact angle diagram of the nonionic Gemini surfactant in this embodiment before and after adding the developer; Figure 3 It can be seen from the comparison that after the non-ionic Gemini surfactant prepared under normal pressure conditions is added to the developer, its interfacial contact angle becomes smaller, indicating that the wettability of the developer is enhanced.

[0070] Example 2

[0071] A method for preparing a nonionic Gemini surfactant under normal pressure comprises the following steps:

[0072] S1, adding 20g of polyethylene glycol monomethyl ether with a molecular weight of 350 and p-toluenesulfonyl chloride into a reaction container, the molar ratio of polyethylene glycol monomethyl ether to p-toluenesulfonyl chloride being 1:1.5, putting into a rotor and adding dichloromethane, stirring evenly, adding triethylamine, the molar ratio of polyethylene glycol monomethyl ether to triethylamine being 1:1.8, reacting at room temperature and normal pressure for 40h, collecting a yellow liquid, i.e., a crude sulfonate; then extracting the crude sulfonate with dichloromethane, the extraction time being 20min, and obtaining a sulfonate after rotary evaporation and drying;

[0073] S2, adding the sulfonate prepared in step S1 into N,N-dimethylformamide, and stirring to obtain a sulfonate solution;

[0074] S3, adding 2g of di-tert-amyl hydroquinone and sodium hydride into a reaction container, the molar ratio of di-tert-amyl hydroquinone to sodium hydride is 1:3.5, replacing the air in the reaction container with an inert gas, placing a rotor and adding N,N-dimethylformamide as a solvent, and stirring at room temperature and normal pressure for 40 minutes, then injecting the sulfonate solution in step S2 into the reaction container with a needle, the molar ratio of di-tert-amyl hydroquinone to sulfonate is 1:3, heating to 85°C at normal pressure and reacting for 30 hours, cooling to 25°C after the reaction is completed, collecting the orange-red liquid, extracting with ethyl acetate, the extraction time is 20 minutes, and rotary drying to obtain a crude product;

[0075] S4. The crude product in step S3 is subjected to column chromatography, wherein the stationary phase of the column chromatography is silica gel powder and the mobile phase is a mixture of dichloromethane and methanol, to obtain a target product, a yellow-red oily liquid, i.e., a nonionic Gemini surfactant.

[0076] like Figure 4 As shown, the infrared spectrum of the nonionic Gemini surfactant of this embodiment:

[0077] 3000-2870cm -1 (peak1) is the stretching vibration absorption peak of aliphatic CH; 1504cm -1 (peak2), 1459cm -1(peak3) is the absorption peak of benzene ring skeleton vibration; 1380cm -1 (peak4) There are two peaks, which are the bending vibration absorption peaks of methyl; 1207cm -1 (peak5) is the stretching vibration absorption peak of CO in phenol; 1150-1060cm -1 (peak6) is the stretching vibration absorption peak of fatty ethers.

[0078] like Figure 5 As shown, the nonionic Gemini surfactant of this embodiment 1 HNMR spectrum:

[0079] 1 HNMR (400MHz, CDCl3) δ6.72 (s, 1H), 4.34–3.26 (m, 34H), 1.83 (dq, J = 14.5, 7.4Hz, 2H), 1.47–1.17 (m, 7H), 0.62 (t, J = 7.3Hz, 3H).

[0080] like Figure 6 As shown in FIG. 1 , the contact angle diagram of the nonionic Gemini surfactant in this embodiment before and after adding the developer; Figure 6 It can be seen from the comparison that after the non-ionic Gemini surfactant prepared under normal pressure conditions is added to the developer, its interfacial contact angle becomes smaller, indicating that the wettability of the developer is enhanced.

[0081] Example 3

[0082] A method for preparing a nonionic Gemini surfactant under normal pressure comprises the following steps:

[0083] S1, adding 20g of polyethylene glycol monomethyl ether with a molecular weight of 500 and p-toluenesulfonyl chloride into a reaction container, the molar ratio of polyethylene glycol monomethyl ether to p-toluenesulfonyl chloride being 1:1.2, putting into a rotor and adding dichloromethane, stirring evenly, adding triethylamine, the molar ratio of polyethylene glycol monomethyl ether to triethylamine being 1:2.2, reacting at room temperature and normal pressure for 35h, collecting a yellow liquid, i.e., a crude sulfonate; then extracting the crude sulfonate with dichloromethane, the extraction time being 30min, and obtaining a sulfonate after rotary evaporation and drying;

[0084] S2, adding the sulfonate prepared in step S1 into N,N-dimethylformamide, and stirring to obtain a sulfonate solution;

[0085] S3, adding 2g of di-tert-amyl hydroquinone and sodium hydride into a reaction container, the molar ratio of di-tert-amyl hydroquinone to sodium hydride is 1:3, replacing the air in the reaction container with an inert gas, placing a rotor and adding N,N-dimethylformamide as a solvent, and stirring at room temperature and normal pressure for 30 minutes, then injecting the sulfonate solution in step S2 into the reaction container with a needle, the molar ratio of di-tert-amyl hydroquinone to sulfonate is 1:2.5, heating to 65°C under normal pressure and reacting for 40 hours, cooling to 15°C after the reaction is completed, collecting the orange-red liquid, extracting with ethyl acetate, the extraction time is 30 minutes, and rotary drying to obtain a crude product;

[0086] S4. The crude product in step S3 is subjected to column chromatography, wherein the stationary phase of the column chromatography is silica gel powder and the mobile phase is a mixture of dichloromethane and methanol, to obtain a target product, a yellow-red oily liquid, i.e., a nonionic Gemini surfactant.

[0087] like Figure 7 As shown, the infrared spectrum of the nonionic Gemini surfactant of this embodiment:

[0088] 3000-2870cm -1 (peak1) is the stretching vibration absorption peak of aliphatic CH; 1504cm -1 (peak2), 1459cm -1 (peak3) is the absorption peak of benzene ring skeleton vibration; 1380cm -1 (peak4) There are two peaks, which are the bending vibration absorption peaks of methyl; 1207cm -1 (peak5) is the stretching vibration absorption peak of CO in phenol; 1150-1060cm -1 (peak6) is the stretching vibration absorption peak of fatty ethers.

[0089] like Figure 8 As shown, the nonionic Gemini surfactant of this embodiment 1 HNMR spectrum:

[0090] 1 HNMR (400MHz, CDCl3) δ6.76 (d, J = 28.2Hz, 1H), 4.19–3.29 (m, 52H), 1.81 (q, J = 7.2Hz, 2H), 1.47–1.15 (m, 7H), 0.62 (t, J = 7.3Hz, 3H).

[0091] like Fig. 9 As shown in FIG. 1 , the contact angle diagram of the nonionic Gemini surfactant in this embodiment before and after adding the developer; Fig. 9It can be seen from the comparison that after the non-ionic Gemini surfactant prepared under normal pressure conditions is added to the developer, its interfacial contact angle becomes smaller, indicating that the wettability of the developer is enhanced.

[0092] The nonionic Gemini surfactant prepared in Example 1-3 was applied to the developer at a concentration of 0.1 g / L. The contact degree and surface tension before and after the developer were tested. The data are shown in Table 1:

[0093] Table 1

[0094]

[0095]

[0096] It can be seen from the data in Table 1 that after the nonionic Gemini surfactant prepared under normal pressure conditions is added, the contact angle and surface tension of the developer solution are significantly reduced.

[0097] Table 2 is an evaluation of the development results before and after the addition of the nonionic Gemini surfactant (concentration of 0.1 g / L) prepared under normal pressure conditions in Examples 1-3 to the semiconductor display wet electronic chemical developer;

[0098] Table 2

[0099]

[0100] Evaluation criteria for development results: A indicates uniform development, B indicates uneven development of some areas, and C indicates uneven development. From the data in Table 2, it can be seen that after the nonionic Gemini surfactant prepared under normal pressure conditions of the present invention is added to the developer, the development result is significantly improved.

[0101] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A nonionic Gemini surfactant, characterized in that: The structural formula of the surfactant is as follows: Wherein, n is a natural number; The preparation method thereof comprises the following steps: S1, adding polyethylene glycol monomethyl ether and p-toluenesulfonyl chloride into a reaction container, then adding a reaction solvent and a catalyst, stirring to react, extracting after the reaction is completed, and rotary evaporation drying to obtain a sulfonate; S2, adding the sulfonate prepared in step S1 into N,N-dimethylformamide, and stirring to obtain a sulfonate solution; S3, adding di-tert-amyl hydroquinone and sodium hydride into a reaction vessel, introducing an inert gas to expel the air, then adding a solvent and stirring evenly, then adding the sulfonate solution in step S2 into the reaction vessel, heating to react, cooling after the reaction is completed, obtaining an orange-red liquid, and then extracting to obtain a crude product; S4. The crude product in step S3 is subjected to column chromatography to obtain a nonionic Gemini surfactant.

2. The nonionic Gemini surfactant according to claim 1, characterized in that: Said n is an integer of 4-11.

3. A method for preparing the nonionic Gemini surfactant according to any one of claims 1 to 2, characterized in that: The following steps are involved: S1, adding polyethylene glycol monomethyl ether and p-toluenesulfonyl chloride into a reaction container, then adding a reaction solvent and a catalyst, stirring to react, extracting after the reaction is completed, and rotary evaporation drying to obtain a sulfonate; S2, adding the sulfonate prepared in step S1 into N,N-dimethylformamide, and stirring to obtain a sulfonate solution; S3, adding di-tert-amyl hydroquinone and sodium hydride into a reaction vessel, introducing an inert gas to expel the air, then adding a solvent and stirring evenly, then adding the sulfonate solution in step S2 into the reaction vessel, heating to react, cooling after the reaction is completed, obtaining an orange-red liquid, and then extracting to obtain a crude product; S4. The crude product in step S3 is subjected to column chromatography to obtain a nonionic Gemini surfactant.

4. The preparation method according to claim 3, characterized in that: In step S1, the reaction solvent is dichloromethane, and the catalyst is triethylamine.

5. The preparation method according to claim 3, characterized in that: In step S1, the molecular weight of the polyethylene glycol monomethyl ether is 200-500; the molar ratio of the polyethylene glycol monomethyl ether to p-toluenesulfonyl chloride is 1:1-1.5; and the molar ratio of the polyethylene glycol monomethyl ether to triethylamine is 1:1.8-2.

2.

6. The preparation method according to claim 3, characterized in that: The stirring reaction conditions in step S1 are to react at room temperature and normal pressure for 30-40 hours.

7. The preparation method according to claim 3, characterized in that: The molar ratio of di-tert-amylhydroquinone to sodium hydride in step S3 is 1:2.5-3.

5.

8. The preparation method according to claim 3, characterized in that: The molar ratio of di-tert-amylhydroquinone to sulfonate in step S3 is 1:2-3.

9. The preparation method according to claim 3, characterized in that: The solvent in step S3 is N,N-dimethylformamide; the heating reaction conditions are at normal pressure and 65-85° C. for 30-40 hours.

10. Use of the nonionic Gemini surfactant as claimed in claim 1 or 2 in wet electronic chemicals, characterized in that: The wet electronic chemical is an etching solution, a stripping solution, a developing solution or a cleaning solution.

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