A fluorine-containing photoresist resin monomer and its preparation method

Abstract

The present invention provides a fluorinated photoresist resin monomer and a preparation method thereof. The fluorinated photoresist resin monomer comprises a structural general formula shown in the following formula I: wherein, R1 is a hydrogen atom or a methyl group; R2 is a hydrogen atom or a C1-C4 perfluoroalkyl group; R3 is a C1-C4 perfluoroalkyl group; 1 ≦ m ≦ 4, 1 ≦ n ≦ 4, and both m and n are positive integers. The preparation method of the fluorinated photoresist resin monomer comprises the following steps: 1) The compound of formula I-1 and the compound of formula I-2 are subjected to a ring-opening esterification reaction to obtain a compound of formula I-3; 2) The reaction product of step a) and a catalyst of the compound of formula I-4 are subjected to an esterification reaction to obtain a compound of formula I. The preparation method of the fluorinated photoresist resin monomer and its intermediate of the present invention has a simple synthesis route, few post-treatment processes, reduces the generation of three wastes, and also greatly improves the purity and yield of the product, with a purity of more than 99% and a yield of more than 88%.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and particularly to a fluorinated photoresist resin monomer and a preparation method thereof. Background Art

[0002] Photoresist, also known as photoresistive agent, refers to a corrosion-resistant thin film material whose solubility changes upon irradiation or radiation by ultraviolet light, electron beam, ion beam, X-ray, etc. Its main components are polymer resin, photoacid generator, and corresponding additives and solvents. Photoresists are classified into two major categories, positive and negative, according to the images they form. In the photoresist process, after coating exposure and development, the exposed part is dissolved and the unexposed part remains. This coating material is a positive photoresist. If the exposed part is retained and the unexposed part is dissolved, this coating material is a negative photoresist. With the development of photoresists, from 365nm, 248nm, 193nm to 193 immersion, the hydrophobicity of photoresists is getting stronger and stronger.

[0003] Resin monomers of fluorine-containing compounds have certain hydrophobicity and are widely used as resin monomers in 193 immersion photoresists. However, due to the influence of the strong electronegativity of fluorine, the more fluorine a monomer contains, the worse its stability. It is prone to decomposition during the reaction and subsequent processing, so the synthesis of high-purity fluorine-containing monomers has always been extremely difficult. Summary of the Invention

[0004] In view of the above-mentioned disadvantages of the prior art, the purpose of the present invention is to provide a fluorinated photoresist resin monomer and a preparation method thereof, with high yield and high purity.

[0005] To achieve the above object and other related objects, the first aspect of the present invention provides a fluorinated photoresist resin monomer: including the structural general formula shown in Formula I below:

[0006] Formula I, where R1 is a hydrogen atom or a methyl group; R2 is a hydrogen atom or a C1-C4 perfluoroalkyl group; R3 is a C1-C4 perfluoroalkyl group; 1 ≤ m ≤ 4, 1 ≤ n ≤ 4, and both m and n are positive integers.

[0007] Due to the influence of the strong electronegativity of fluorine, fluorinated photoresist resin monomers are generally not very stable, which is determined by the physical and chemical properties of the substance itself. The stability referred to in the present invention means that the substance is relatively stable under the reaction conditions (such as types of materials, molar ratios, temperature, solvents, etc.) and post-treatment purification methods, and is not as easily decomposed or polymerized as under other ordinary conditions. It deteriorates while being purified, reaching a dynamic equilibrium, thus affecting the purity of the final product. The present invention well solves this problem.

[0008] Further, it further includes at least one of the following technical features:

[0009] a1) R2 is selected from one of a hydrogen atom, a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group; preferably, R2 is selected from one of a hydrogen atom, a perfluoromethyl group, or a perfluoroethyl group.

[0010] a2) R3 is selected from one of a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group; preferably, R3 is a perfluoromethyl group.

[0011] a3) 2 ≤ m ≤ 4, where m is a positive integer; preferably, m is 2;

[0012] a4) 2 ≤ n ≤ 4, where n is a positive integer; preferably, n is 2;

[0013] More preferably, Formula I specifically includes the following structures:

[0014]

[0015] The second invention of the present invention provides a method for preparing a fluorinated photoresist resin, including the following steps:

[0016] 1) The compound of Formula I-1 and the compound of Formula I-2 are subjected to a ring-opening esterification reaction to obtain the compound of Formula I-3;

[0017] 2) The reaction product of step 1) is subjected to an esterification reaction with the compound of Formula I-4 and a catalyst to obtain the compound of Formula I;

[0018] The reaction route is as follows:

[0019]

[0020] Among them, R1 is a hydrogen atom or a methyl group; R2 is a hydrogen atom or a perfluoroalkyl group with 1 to 4 carbon atoms; R3 is a perfluoroalkyl group with 1 to 4 carbon atoms; 1 ≤ m ≤ 4, 1 ≤ n ≤ 4, and m and n are positive integers.

[0021] The fluorinated photoresist resin monomer itself is not very stable; this condition avoids using conventional conditions that would cause the monomer to change, such as strong acids, strong bases, high temperatures, and other severe conditions. The reaction conversion rate is high, and the post-treatment is simple without using conventional impurity removal means such as strong acid washing and strong base washing. Therefore, considering the mild reaction conditions and post-treatment conditions, the reaction conversion rate and the yield of the final product are improved.

[0022] Further, in step 1), it further includes at least one of the following technical features:

[0023] 11) The molar ratio of the compound of Formula I-1 to the compound of Formula I-2 is 1:1 to 1:2, preferably 1:1.5;

[0024] 12) The temperature of the ring-opening esterification reaction is 5 to 50 °C, preferably 45 to 50 °C;

[0025] 13) The time of the ring-opening esterification reaction is 6 to 20 h, preferably 16 h;

[0026] 14) Step 1) further includes the following steps: adding organic solvent A to the reaction product of step 1), filtering, concentrating the filtrate, and drying.

[0027] Further, in feature 15), it further includes at least one of the following technical features:

[0028] 141) The organic solvent A is selected from one of methyl tert-butyl ether, ethyl acetate, and dichloromethane.

[0029] 142) The filtration is carried out using diatomaceous earth filtration;

[0030] Further, in step 2), it further includes at least one of the following technical features:

[0031] 21) The molar ratio of the compound of formula I-3 to the compound of formula I-4 is 1:1.0 to 2.0;

[0032] 22) The reaction solvent for the esterification reaction is selected from one of dichloromethane, tetrahydrofuran, acetonitrile, and N,N-dimethylformamide;

[0033] 23) The catalyst is selected from one of DCC, EDCI, HATU, and CDI;

[0034] 24) The addition temperature of the catalyst is controlled at 0 to 5 °C;

[0035] 25) The esterification reaction is first carried out at 0 to 5 °C for 2 h, and then at 20 to 30 °C for 6 to 20 h;

[0036] 26) Step 2) further includes the following steps: filtering the reaction product of step 2) for the first time, concentrating the first filtrate, adding organic solvent B and filtering for the second time, concentrating the second filtrate, and carrying out vacuum distillation.

[0037] Further, in feature 26), it further includes at least one of the following technical features:

[0038] 261) The organic solvent B is selected from one of petroleum ether, n-hexane, and n-heptane;

[0039] 262) The second filtration is carried out using silica gel or neutral alumina;

[0040] Compared with the prior art, the synthetic route of the present application is simple, with fewer post-treatment processes, reducing the generation of three wastes. At the same time, the purity and yield of the product are greatly improved, with a purity of over 99% and a yield of over 88%. Description of the Drawings

[0041] Figure 1 It is the HNMR spectrum of the product prepared in Example 1;

[0042] Figure 2 It is the HNMR spectrum of the product prepared in Example 2;

[0043] Figure 3 It is the FNMR spectrum of the product prepared in Example 2. Detailed Embodiments

[0044] The technical solutions of the present invention will be further specifically described below through specific examples. It should be understood that the implementation of the present invention is not limited to the following examples, and any formal modification and / or change made to the present invention will fall within the protection scope of the present invention.

[0045] In the present invention, the equipment and raw materials used can be purchased from the market or are commonly used in the art. The methods in the following examples are all conventional methods in the art unless otherwise specified.

[0046] Example 1

[0047]

[0048] After purging the 500 mL reaction flask with nitrogen, hydroxyethyl methacrylate (100 g, 0.77 mol) and succinic anhydride (115 g, 1.15 mol) were added, and the temperature was raised to 45 - 50 °C and stirred for 16 h. After the reaction was completed, the temperature was lowered to room temperature, methyl tert-butyl ether was added, and the temperature was further lowered to -10 - 20 °C and stirred. It was filtered through diatomaceous earth, and the filtrate was concentrated and dried with an oil pump to obtain 169 g of a crude product as a pale yellow viscous liquid, with a yield of 95.5%. The obtained crude product was directly fed into the next step without further purification.

[0049] After purging the 1-L reaction flask with nitrogen, the above-mentioned crude product (100 g) and dichloromethane (500 mL) were added. The temperature was lowered to 0 - 5 °C, and then hexafluoroisopropanol (87.59 g, 0.52 mol) was added. After stirring for 10 min, N,N'-dicyclohexylcarbodiimide DCC (107.55 g, 0.52 mol) was added while controlling the temperature at 0 - 5 °C. Stirring was maintained at 0 - 5 °C for 2 h, and then the temperature was slowly raised to room temperature and stirred for 16 h. After the reaction was completed, the solid insoluble matter was removed by filtration. The obtained filtrate was concentrated to dryness, then petroleum ether was added and stirred to dissolve. It was filtered through silica gel, and the obtained filtrate was concentrated to dryness to obtain a crude light yellow liquid. After purification by vacuum distillation, a pure colorless liquid (146 g, 0.38 mol) was obtained, with a yield of 88.4% and a GC purity of 99%. The HNMR spectrum is shown in Figure 1 。

[0050] Example 2

[0051]

[0052] After purging the 500-mL reaction flask with nitrogen, 2-hydroxyethyl methacrylate (100 g, 0.77 mol)) and succinic anhydride (115 g, 1.15 mol) were added. The temperature was raised to 45 - 50 °C and stirred for 16 h. After the reaction was completed, the temperature was lowered to room temperature, methyl tert-butyl ether was added, and the temperature was further lowered to -10 - -20 °C and stirred. It was filtered through diatomaceous earth, and the filtrate was concentrated and dried with an oil pump to obtain 169 g of a crude light yellow viscous liquid, with a yield of 95.5%. The obtained crude product was directly used for the next step without further purification.

[0053] After purging the 1-L reaction flask with nitrogen, the above-mentioned crude product (100 g) and dichloromethane (500 mL) were added. The temperature was lowered to 0 - 5 °C, and then pentafluoropropanol (78.21 g, 0.52 mol) was added. After stirring for 10 min, DCC (107.55 g, 0.52 mol) was added while controlling the temperature at 0 - 5 °C. Stirring was maintained at 0 - 5 °C for 2 h, and then the temperature was slowly raised to room temperature and stirred for 16 h. After the reaction was completed, the solid insoluble matter was removed by filtration. The obtained filtrate was concentrated to dryness, then petroleum ether was added and stirred to dissolve. It was filtered through silica gel, and the obtained filtrate was concentrated to dryness to obtain a crude light yellow liquid. After purification by vacuum distillation, a pure colorless liquid (151 g, 0.42 mol) was obtained, with a yield of 95.9% and a GC purity of 99%. The HNMR spectrum is shown in Figure 2 , and the FNMR spectrum is shown in Figure 3 。

[0054] The above embodiments are only illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Any person familiar with this technology can modify or change the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes made by those with ordinary knowledge in the technical field without departing from the spirit and technical idea disclosed by the present invention should still be covered by the claims of the present invention.

Claims

1. A preparation method of a fluorine-containing photoresist resin monomer, characterized in that, it comprises the following steps: 1) The compound of formula I-1 and the compound of formula I-2 are subjected to a ring-opening esterification reaction. An organic solvent A is added to the reaction product, stirred, filtered, the filtrate is concentrated, dried, and the compound of formula I-3 is obtained; the temperature of the ring-opening esterification reaction is 5-50 °C; the stirring temperature is -10 to -20 °C; the organic solvent A is selected from one of methyl tert-butyl ether, ethyl acetate, and dichloromethane; 2) The reaction product of step 1) is subjected to an esterification reaction with the compound of formula I-4 and a condensing agent. The reaction product is subjected to a first filtration, the first filtrate is concentrated, an organic solvent B is added for a second filtration, the second filtrate is concentrated, and vacuum distilled to obtain the compound of formula I; the addition temperature of the condensing agent is controlled at 0-5 °C; the esterification reaction is first carried out at 0-5 °C for 2 h, and then at 20-30 °C for 6-20 h; the condensing agent is DCC; the reaction solvent for the esterification reaction is selected from one of dichloromethane, tetrahydrofuran, acetonitrile, and N,N-dimethylformamide; the organic solvent B is selected from one of petroleum ether, n-hexane, and n-heptane; The reaction route is as follows: Among them, R 1 is a hydrogen atom or a methyl group; R 2 is a hydrogen atom or a C1-C4 perfluoroalkyl group; R 3 is a C1-C4 perfluoroalkyl group; 1 ≤ m ≤ 4, 1 ≤ n ≤ 4, and m and n are positive integers; the molar ratio of the compound of formula I-3 to the compound of formula I-4 is 1:1.0 to 2.

0.

2. The preparation method of the fluorine-containing photoresist resin monomer according to claim 1, characterized in that, in step 1), it further comprises at least one of the following technical features: the molar ratio of the compound of formula I-1 to the compound of formula I-2 is 1:1 to 1:2; the time of the ring-opening esterification reaction is 6-20 h.

3. The preparation method of the fluorine-containing photoresist resin monomer according to claim 1, characterized in that, in step 1), the filtration is carried out using diatomaceous earth filtration.

4. The preparation method of the fluorine-containing photoresist resin monomer according to claim 1, characterized in that, the second filtration is carried out using one of silica gel and neutral alumina.

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