A photoresist main resin synthesis intermediate and preparation method thereof

Abstract

The present invention belongs to the field of chemical synthesis and photolithography materials, and specifically relates to a photoresist main resin synthesis intermediate and a preparation method thereof. The photoresist main resin in the present invention is a 193 nm photoresist main resin, and the photoresist main resin synthesis intermediate is an adamantane derivative, i.e., 3-(adamantane-1-oxy)-2-thiophene methanol, specifically, 1-bromo-adamantane is used as a raw material, and under alkaline conditions, after reacting with 3-hydroxy-2-thiophene carboxylic acid methyl ester, 3-(adamantane-1-oxy)-2-thiophene carboxylic acid methyl ester is first obtained, and then the obtained 3-(adamantane-1-oxy)-2-thiophene carboxylic acid methyl ester is reduced under the action of LiAlH4, and finally 3-(adamantane-1-oxy)-2-thiophene carboxylic acid methyl ester is obtained. The beneficial effects of the present invention are: (1) the synthesis reaction is safe and reliable, the process is simple, easy to control, and easy to realize large-scale industrial production; (2) the reaction yield is high; (3) the etching resistance is excellent.

Description

Technical Field

[0001] The invention belongs to the field of chemical synthesis and photolithography materials, and in particular relates to a photoresist main resin synthesis intermediate and a preparation method thereof. Background Art

[0002] Photoresist main resin is mainly used for fine pattern processing of integrated circuits and discrete semiconductor devices. It is a key material for ultra-large-scale integrated circuits in the electronic information industry. In addition to being widely used in the manufacturing of electronic products such as mobile phones and computers, it also has important applications in aerospace, military technology and other fields.

[0003] Among them, the 193nm photoresist main resin is the key material of photoresist, and the market demand is very large. It is mainly used in immersion lithography. Therefore, the photoresist main resin needs to have good etching resistance. However, at this stage, the photoresist resin technology still has problems such as cracks, rough surface, and film swelling caused by partial dissolution of the film in the non-exposed area. These defects can only be solved by continuously improving its main resin structure and then changing its performance.

[0004] In the prior art, acrylic acid or methacrylate polymers are widely used in the preparation of photoresist main resins due to their high transparency. However, the etching resistance of such resins is limited. The main reason is that the main chain of the main resin is generally a methylene polymer formed by acrylic acid or methacrylate monomers, which is mainly used to provide film-forming properties and mechanical properties required by the processing process. Therefore, the corrosion resistance is relatively limited. The improvement of the resin corrosion resistance is mainly achieved by modifying the side chain. Generally speaking, the higher the carbon-hydrogen ratio of the photoresist main resin, the better the etching resistance. Therefore, modifying high-carbon organic compounds on the photoresist resin monomer has become a hot topic in current research.

[0005] Adamantane derivatives have the characteristics of high carbon content and stable chemical properties, providing high etching resistance, and are widely used in the design of photoresist main resin structure. For example, the photoresist main resin represented by methacrylate polymers. At present, the synthesis of its etching-resistant resin monomer is mainly through: using adamantane ketone as a raw material, reacting with Grignard reagent to generate a strongly alkaline magnesium salt, adding a catalyst to react it with methacryloyl chloride to generate the corresponding adamantane methacrylate monomer.

[0006] However, the above-mentioned technology of using adamantane ketone as a raw material to prepare the synthetic intermediate of the main resin has problems such as low raw material cost and stringent reaction conditions.

[0007] In addition, as an important intermediate for synthesizing adamantane acrylate monomer, adamantane alcohol has the advantages of moderate reaction temperature and relatively easy availability of raw materials, which completely avoids the occurrence of the above-mentioned problems. However, the adamantane alcohol prepared by the existing technology still has problems such as low yield and even inconvenient post-processing. For example, the classic preparation method of adamantane alcohol is the halogenation hydrolysis method, that is, adamantane is used as a raw material, a halogenated adamantane is first synthesized by a halogenation reaction, and then hydrolyzed to obtain adamantane alcohol, but this method consumes a lot of halogen and produces a large amount of three wastes; in addition, adamantane is used as a raw material, and adamantane alcohol or adamantane polyol can be directly obtained under the action of an oxidant, but this method has harsh reactions and is difficult to achieve large-scale industrial production.

[0008] Therefore, there is an urgent need for a photoresist main resin synthesis intermediate with high yield, convenient post-processing, environmental friendliness and suitability for industrial production. Summary of the invention

[0009] In order to solve the above technical problems, the present invention provides a photoresist main resin synthesis intermediate and a preparation method thereof.

[0010] The photoresist main resin synthesis intermediate provided by the present invention is 3-(adamantane-1-oxy)-2-thiophene methanol. The preparation method of the intermediate has the advantages of safe and reliable synthesis reaction, simple process, easy reaction control, high yield, etc. The total yield of the two-step reaction can reach more than 77%.

[0011] The specific technical solutions of the present invention are as follows:

[0012] A photoresist main resin synthesis intermediate, the synthesis intermediate is an adamantane derivative 3-(adamantane-1-oxy)-2-thiophene methanol, which is obtained by taking 1-bromo-adamantane as a raw material, reacting with 3-hydroxy-2-thiophenecarboxylic acid methyl ester under alkaline conditions, and then reducing the obtained compound.

[0013] In particular, the main preparation steps of the photoresist main resin synthesis intermediate are as follows:

[0014] Step (I): using 1-bromo-adamantane as a raw material, reacting with 3-hydroxy-2-thiophenecarboxylic acid methyl ester under alkaline conditions to obtain 3-(adamantane-1-oxy)-2-thiophenecarboxylic acid methyl ester;

[0015] Step (II): reducing the methyl 3-(adamantane-1-oxy)-2-thiophenecarboxylate obtained in step (I) to generate 3-(adamantane-1-oxy)-2-thiophenecarboxylate.

[0016] In particular, the reaction formula for preparing the synthetic intermediate is as follows:

[0017]

[0018] Preferably, the photoresist main resin is a 193nm photoresist main resin.

[0019] The present invention also provides a photoresist main body resin containing the synthetic intermediate 3-(adamantane-1-oxyl)-2-thiophene carbinol structure, which is also one of the key points protected by the present invention.

[0020] The present invention also provides a method for preparing the photoresist main resin synthetic intermediate, which specifically comprises the following steps:

[0021] Step S1, adding methyl 3-hydroxy-2-thiophenecarboxylate to dried tetrahydrofuran, gradually adding NaH at room temperature, stirring, adding 1-bromo-adamantane, stirring at room temperature for 5-7 hours, adding NaOH solution, stirring, adding an organic solvent for extraction, separating the liquids, and obtaining an upper organic layer;

[0022] Step S2, evaporating the organic layer obtained in step S1 under reduced pressure to dryness to obtain a crude product, and purifying to obtain 3-(adamantane-1-oxy)-2-thiophenecarboxylic acid methyl ester as a white solid;

[0023] Step S3, adding LiAlH4 to dried tetrahydrofuran, adding the white solid 3-(adamantane-1-oxy)-2-thiophenecarboxylic acid methyl ester obtained in step S2 at room temperature, stirring, and performing a reduction reaction;

[0024] Step S4, after the reaction mixture in step S3 is cooled, NaOH solution is added, stirred, filtered, and the filtrate is evaporated to dryness under reduced pressure to obtain 3-(adamantane-1-oxy)-2-thiophenemethanol as a white solid.

[0025] Preferably, in step S1, the mass fraction of the NaOH solution is 4-6%, and the added volume is 15-35 mL.

[0026] Preferably, in step S1, the organic solvent is ethyl acetate.

[0027] Preferably, in step S2, the purification condition is: purifying the crude product by silica gel column chromatography with ethyl acetate: petroleum ether = 1:8-12 volume ratio as the mobile phase.

[0028] Preferably, in step S2, the purification condition is: purifying the crude product by silica gel column chromatography with ethyl acetate: petroleum ether = 1:10 as the mobile phase.

[0029] Preferably, in step S4, the mass fraction of the NaOH solution is 8-12%, and the added amount is 0.2-0.3 mL.

[0030] The beneficial effects of the present invention are as follows:

[0031] (1) The synthesis reaction is safe and reliable, and the process is simple. Compared with the prior art process of using adamantane as a raw material to obtain adamantane alcohol or adamantane polyol under the action of an oxidant, the process is easy to control and facilitates large-scale industrial production.

[0032] (2) The reaction yield is high. During the preparation process, the yield of the intermediate product 3-(adamantane-1-oxy)-2-thiophenecarboxylic acid methyl ester can reach 84%. In the second step of reduction reaction, the yield of 3-(adamantane-1-oxy)-2-thiophene methanol reaches 92%.

[0033] In summary, the present invention uses 1-bromo-adamantane as a raw material, and reacts with 3-hydroxy-2-thiophenecarboxylic acid methyl ester under alkaline conditions to obtain 3-(adamantane-1-oxy)-2-thiophene methanol. The method is environmentally friendly, convenient for post-treatment, high in yield, and has good prospects for large-scale production. DETAILED DESCRIPTION

[0034] The principles of preparing methyl 3-(adamantane-1-oxy)-2-thiophenecarboxylate in Examples 1-5 are shown in the following reaction formula:

[0035]

[0036] Example 1

[0037] 2.4 g (15 mmol) of methyl 3-hydroxy-2-thiophenecarboxylate was added to 30 mL of dried tetrahydrofuran, and 0.40 g (about 17 mmol) of NaH was gradually added at room temperature, and stirred for 20 min; 3.3 g of 1-bromo-adamantane (15 mmol) was added to the reaction mixture, and stirring was continued at room temperature for 6 h, and then 20 mL of 5% NaOH solution was added, and the mixture was fully stirred, and then extracted three times with 20 mL of ethyl acetate. The extract was dried and evaporated to dryness under reduced pressure to obtain 4.0 g of a crude product.

[0038] The obtained crude product was purified by silica gel column chromatography (ethyl acetate:petroleum ether, 1:10 v / v) to obtain 3.7 g of methyl 3-(adamantane-1-oxy)-2-thiophenecarboxylate as a white solid with a yield of 84%.

[0039] Example 2

[0040] 2.4 g (15 mmol) of methyl 3-hydroxy-2-thiophenecarboxylate was added to 30 mL of dried tetrahydrofuran, and 0.42 g (about 17 mmol) of NaH was gradually added at room temperature. The mixture was stirred for 20 min, and 3.3 g of 1-bromo-adamantane (15 mmol) was added to the reaction mixture. The mixture was stirred at room temperature for 24 h, and 20 mL of 5.5% NaOH solution was added. The mixture was stirred thoroughly, and then extracted three times with 20 mL of ethyl acetate. The extract was dried and evaporated to dryness under reduced pressure to obtain 4.0 g of a crude product.

[0041] The crude product was purified by silica gel column chromatography (ethyl acetate:petroleum ether, 1:10 v / v) to obtain 3.6 g of methyl 3-(adamantane-1-oxy)-2-thiophenecarboxylate as a white solid with a yield of 83%.

[0042] Example 3

[0043] 2.4 g (15 mmol) of methyl 3-hydroxy-2-thiophenecarboxylate was added to 30 mL of dried tetrahydrofuran, and 0.42 g (about 17 mmol) of NaH was gradually added at room temperature. The mixture was stirred for 20 min, and 3.3 g of 1-bromo-adamantane (15 mmol) was added to the reaction mixture. The mixture was stirred at room temperature for 4 h, and 20 mL of 5.5% NaOH solution was added. The mixture was stirred thoroughly, and then extracted three times with 20 mL of ethyl acetate. The extract was dried and evaporated to dryness under reduced pressure to obtain 3.9 g of a crude product.

[0044] The crude product was purified by silica gel column chromatography (ethyl acetate:petroleum ether, 1:10 v / v) to obtain 3.4 g of methyl 3-(adamantane-1-oxy)-2-thiophenecarboxylate as a white solid with a yield of 78%.

[0045] Example 4

[0046] 2.4 g (15 mmol) of methyl 3-hydroxy-2-thiophenecarboxylate was added to 30 mL of dried tetrahydrofuran, and 0.47 g (about 20 mmol) of NaH was gradually added at room temperature, and stirred for 20 min. 4.4 g of 1-bromo-adamantane (20 mmol) was added to the reaction mixture, and stirring was continued for 6 h at room temperature, and then 20 mL of 5% NaOH solution was added, and the mixture was fully stirred, and then extracted three times with 20 mL of ethyl acetate. The extract was dried and evaporated to dryness under reduced pressure to obtain 4.1 g of crude product.

[0047] The crude product was purified by silica gel column chromatography (ethyl acetate:petroleum ether, 1:10 v / v) to obtain 3.8 g of methyl 3-(adamantane-1-oxy)-2-thiophenecarboxylate as a white solid with a yield of 86%.

[0048] Example 5

[0049] 2.4 g (15 mmol) of methyl 3-hydroxy-2-thiophenecarboxylate was added to 30 mL of dried tetrahydrofuran, and 0.35 g (about 15 mmol) of NaOH was gradually added at room temperature, and stirred for 20 min. 3.3 g of 1-bromo-adamantane (15 mmol) was added to the reaction mixture, and stirring was continued for 6 h at room temperature, and then 20 mL of 5% NaOH solution was added, and the mixture was fully stirred, and then extracted with 20 mL of ethyl acetate for three times. The extract was dried and evaporated to dryness under reduced pressure to obtain 3.8 g of crude product.

[0050] The crude product was purified by silica gel column chromatography (ethyl acetate:petroleum ether, 1:10 v / v) to obtain 3.3 g of methyl 3-(adamantane-1-oxy)-2-thiophenecarboxylate as a white solid with a yield of 75%.

[0051] The above-mentioned Example 2 greatly prolonged the reaction time on the basis of Example 1, and the reaction time was 24 hours, but the yield remained basically unchanged; in Example 3, the reaction time was 4 hours, and the yield was 6% lower than that of Example 1, so the reaction was basically complete after a reaction time of 6 hours.

[0052] In Example 4, the amount of NaH is increased relative to Example 1 (the molar ratio of NaH to the raw material is 1:1.3), and the yield does not change much. In Example 5, the amount of NaH is reduced relative to Example 1 (the molar ratio of NaH to the raw material is 1:1), and the yield decreases significantly, indicating that a molar ratio of NaH to the raw material of 1:1.13 can indeed achieve better technical effects.

[0053] Embodiment 6-7

[0054] The following Examples 6-7 are reduction reactions for preparing adamantane derivatives 3-(adamantane-1-oxy)-2-thiophene methanol, and the principle is shown in the following reaction formula:

[0055]

[0056] Example 6

[0057] 0.38 g (10 mmol) of LiAlH4 was added to 20 mL of dried tetrahydrofuran, and 2.9 g (10 mmol) of methyl 3-(adamantane-1-oxy)-2-thiophenecarboxylate was gradually added at room temperature. The mixture was stirred for 2 h at room temperature, and 0.20 mL of 10% NaOH aqueous solution was added. The mixture was vigorously stirred for 10 min and then filtered. The solution was evaporated under reduced pressure to give 2.4 g of 3-(adamantane-1-oxy)-2-thiophenemethanol as a white solid with a yield of 92%.

[0058] Example 7

[0059] 0.46 g (12 mmol) of LiAlH4 was added to 20 mL of dried tetrahydrofuran, and 2.9 g (10 mmol) of methyl 3-(adamantane-1-oxy)-2-thiophenecarboxylate was gradually added at room temperature. The mixture was stirred for 2 h at room temperature, and 0.20 mL of 10% NaOH aqueous solution was added. The mixture was vigorously stirred for 10 min and then filtered. The solution was evaporated under reduced pressure to give 2.3 g of 3-(adamantane-1-oxy)-2-thiophenemethanol as a white solid with a yield of 88%.

[0060] Example 8

[0061] 0.30 g (8 mmol) of LiAlH4 was added to 20 mL of dried tetrahydrofuran, and 2.9 g (10 mmol) of methyl 3-(adamantane-1-oxy)-2-thiophenecarboxylate was gradually added at room temperature. The mixture was stirred for 2 h at room temperature, and 0.20 mL of 10% NaOH aqueous solution was added. The mixture was vigorously stirred for 10 min and then filtered. The solution was evaporated under reduced pressure to give 2.1 g of 3-(adamantane-1-oxy)-2-thiophenemethanol as a white solid with a yield of 82%.

[0062] Example 9

[0063] 0.46 g (12 mmol) of LiAlH4 was added to 20 mL of dried tetrahydrofuran, and 2.9 g (10 mmol) of methyl 3-(adamantane-1-oxy)-2-thiophenecarboxylate was gradually added at room temperature. The mixture was stirred for 2 h at room temperature, and 0.40 mL of 10% NaOH aqueous solution was added. The mixture was vigorously stirred for 10 min and then filtered. The solution was evaporated under reduced pressure to give 2.0 g of 3-(adamantane-1-oxy)-2-thiophenemethanol as a white solid with a yield of 77%.

[0064] In the above-mentioned Examples 6-9, Example 7 increases the amount of LiAlH4 compared to Example 6 (the molar ratio of LiAlH4 to the raw material is 1.2:1), and the yield is slightly reduced. The main reason may be that the excess LiAlH4 forms more solid Al(OH)3 during post-treatment, and Al(OH)3 is a colloidal precipitate, so it has certain adsorption properties, and the adsorption of the product increases, which in turn reduces the yield.

[0065] In Example 8, the amount of LiAlH4 is reduced compared to Example 6 (the molar ratio of LiAlH4 to the raw material is 0.8:1), and the yield is significantly reduced, that is, a molar ratio of LiAlH4 to the raw material of 1:1 can achieve better results.

Claims

1. A photoresist main resin synthesis intermediate, characterized in that: The synthetic intermediate is an adamantane derivative 3-(adamantane-1-oxy)-2-thiophene methanol, which is obtained by taking 1-bromo-adamantane as a raw material and reacting it with 3-hydroxy-2-thiophenecarboxylic acid methyl ester under alkaline conditions, and then reducing the obtained compound.

2. A photoresist main resin synthesis intermediate as claimed in claim 1, characterized in that: The main preparation steps of the synthetic intermediate are as follows: Step (I): under alkaline conditions, using 1-bromo-adamantane as a raw material, reacting with 3-hydroxy-2-thiophenecarboxylic acid methyl ester to obtain 3-(adamantane-1-oxy)-2-thiophenecarboxylic acid methyl ester; Step (II): reducing the methyl 3-(adamantane-1-oxy)-2-thiophenecarboxylate obtained in step (I) to generate 3-(adamantane-1-oxy)-2-thiophenecarboxylate.

3. A photoresist main resin synthesis intermediate as claimed in claim 1, characterized in that: The reaction formula in the preparation process of the synthetic intermediate is as follows: 。 4. A photoresist main resin synthesis intermediate as claimed in claim 1, characterized in that: The photoresist main resin is a 193nm photoresist main resin.

5. A photoresist main body resin containing the photoresist main body resin synthesis intermediate according to claim 1.

6. A method for preparing a photoresist main resin synthesis intermediate, characterized in that: The specific steps include: Step S1, adding methyl 3-hydroxy-2-thiophenecarboxylate to dried tetrahydrofuran, gradually adding NaH at room temperature, stirring, adding 1-bromo-adamantane, stirring at room temperature for 5-7 hours, adding NaOH solution, stirring sufficiently, adding an organic solvent for extraction, separating the liquids, and obtaining an upper organic layer; Step S2, evaporating the organic layer obtained in step S1 under reduced pressure to dryness to obtain a crude product, and purifying to obtain 3-(adamantane-1-oxy)-2-thiophenecarboxylic acid methyl ester as a white solid; Step S3, adding LiAlH4 to dried tetrahydrofuran, adding the white solid 3-(adamantane-1-oxy)-2-thiophenecarboxylic acid methyl ester obtained in step S2 at room temperature, stirring, and performing a reduction reaction; Step S4, after the reaction mixture in step S3 is cooled, NaOH solution is added, stirred, filtered, and the filtrate is evaporated to dryness under reduced pressure to obtain 3-(adamantane-1-oxy)-2-thiophenemethanol as a white solid.

7. The method for preparing a photoresist main resin synthetic intermediate according to claim 6, characterized in that: In step S1, the mass fraction of the NaOH solution is 4-6%, and the added volume is 15-35 mL.

8. The method for preparing a photoresist main resin synthetic intermediate according to claim 6, characterized in that: In step S1, the organic solvent is ethyl acetate.

9. The method for preparing a photoresist main resin synthetic intermediate according to claim 6, characterized in that: In step S2, the purification condition is: the crude product is purified by silica gel column chromatography using ethyl acetate: petroleum ether = 1:8-12 volume ratio as the mobile phase.

10. The method for preparing a photoresist main resin synthetic intermediate according to claim 6, characterized in that: In step S4, the mass fraction of the NaOH solution is 8-12%, and the added amount is 0.2-0.3 mL.

Images