A method for preparing a photoresist resin monomer containing a lactone structure
A controlled reaction process for synthesizing photoresist resin monomers with lactone structures enhances yield and purity by using precise temperature and solvent conditions, addressing the inefficiencies of previous methods.
Patent Information
- Application Number
- CN202111614484.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2021-12-27
- Publication Date
- 2024-12-27
- Estimated Expiration
- 2041-12-27
AI Technical Summary
Existing methods for preparing photoresist resin monomers with lactone structures suffer from low yield and purity due to reactions conducted in non-inert environments without polymerization inhibitors.
A controlled reaction process involving specific temperature and solvent conditions, including ring-opening and esterification steps, is employed to synthesize the photoresist resin monomer, utilizing compounds like 4-pentenoic acid, formic acid, methanol, concentrated hydrochloric acid, and methacryloyl chloride, with careful purification using silica gel columns and specific solvent mixtures.
The method achieves high yield and high purity of the photoresist resin monomer by minimizing impurity formation, thereby improving the product's quality and efficiency.
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Figure CN114315766B_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of photoresists, and in particular to a method for preparing a photoresist resin monomer containing a lactone structure. Background Art
[0002] 193nm photoresist is basically a chemically amplified photoresist, which is a photoresist based on the principle of chemical amplification. Its main components are polymer resin, photoacid generator, corresponding additives (alkaline additives, dissolution inhibitors, etc.) and solvent. Among them, the polymer resin is formed by copolymerization between resin monomers with different side chain structures. The side chain structure is a key component that gives the polymer resin the required functions, and usually provides polar groups and acid-sensitive groups for the polymer resin. The polar group can balance the hydrophilicity and hydrophobicity of the resin, improve the adhesion between the resin and the substrate, and provide developability for the main resin. The acid-sensitive group can be detached from the side chain under the action of the photoacid generator, so that the resin changes from insoluble to alkali soluble, and the solubility contrast between the exposed area and the unexposed area is achieved. Among them, the polar groups include hydroxyl, carboxyl, lactone (such as 1,4-butyrolactone, δ-cyclopentanolactone, β,β-dimethyl-γ-butyrolactone), etc.
[0003] Taiwan Patent TW090113945 discloses a method for preparing a positive photoresist resin monomer 4-methacryloyloxymethyl-γ-butyrolactone. When preparing the resin monomer, the reaction is not carried out in an inert environment, and no polymerization inhibitor is added to the product, resulting in a very low yield of the product. Therefore, the art is in urgent need of a method for preparing a photoresist resin monomer containing a lactone structure. Summary of the invention
[0004] The purpose of the present invention is to overcome the defects of the prior art and provide a method for preparing a photoresist resin monomer containing a lactone structure.
[0005] In order to achieve the purpose of the present invention, this application provides the following technical solutions.
[0006] In a first aspect, the present application provides a method for preparing a photoresist resin monomer containing a lactone structure, and the reaction route of the preparation method is as follows:
[0007]
[0008] Wherein, R1 and R2 are hydrogen atoms or alkyl groups respectively;
[0009] Preferably, R1 and R2 are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
[0010] The preparation method comprises the following steps:
[0011] a) mixing the compound of formula IV and formic acid, and continuously introducing oxygen at a temperature of 50 to 60° C. to react to obtain an intermediate;
[0012] b) adding methanol and concentrated hydrochloric acid to the intermediate obtained in step a), subjecting it to a ring-opening reaction, and purifying it to obtain a compound of formula III;
[0013] c) adding the compound of formula III obtained in step b) into an organic solvent, adding an acid-binding agent, and then dropwise adding the compound of formula II, subjecting it to esterification reaction and purification, to obtain the compound of formula I.
[0014] In one embodiment of the first aspect, the preparation method further includes at least one of the following technical features:
[0015] a1) In step a), the molar ratio of the compound of formula IV to oxygen is 1:(3-5), such as 1:9 or 1:3 or 1:4 or 1:5;
[0016] a2) in step a), the concentration of formic acid is 85 wt%;
[0017] a3) In step a), the time for introducing oxygen is 4 to 6 hours, such as 4 hours or 5 hours.
[0018] In one embodiment of the first aspect, the preparation method further includes at least one of the following technical features:
[0019] b1) in step b), the mass ratio of methanol to concentrated hydrochloric acid is (80-100):1, such as 85:1 or 90:1 or 95:1;
[0020] b2) in step b), the concentration of concentrated hydrochloric acid is 36wt%;
[0021] b3) In step b), the ring-opening reaction is carried out at a temperature of 20 to 30°C, such as 25°C or 27°C, and for a time of 1.5 to 3 hours, such as 2 hours or 2.5 hours.
[0022] In one embodiment of the first aspect, the product purification b4) in step b) comprises the following steps: concentrating the mixed solution after the reaction under reduced pressure and draining the oil pump.
[0023] In one embodiment of the first aspect, the purification b4) further comprises at least one of the following technical features:
[0024] b41) In step b4), the temperature used for the reduced pressure concentration is 25-45°C, such as 32°C or 40°C; the pressure is 0.01-0.03MP, such as 0.02MP;
[0025] b42) In step b4), the oil bath temperature of the oil pump is 25-45°C, such as 32°C or 40°C; the pressure is 20-130Pa, such as 50Pa or 70Pa or 100Pa.
[0026] In one embodiment of the first aspect, the preparation method further includes at least one of the following technical features:
[0027] c1) In step c), the molar ratio of the compound of formula III, the acid binding agent and the compound of formula II is 1:(1-2):(1-2), such as 1:1.1:1.05 or 1:1.2:1.3 or 1:1.5:1.6 or 1:1.8:1.8;
[0028] c2) in step c), the temperature used for adding the acid binding agent is -55°C to -65°C, such as -60°C or -63°C;
[0029] c3) In step c), the temperature used for dropwise addition of the compound of formula II is -55°C to -65°C, such as -60°C or -63°C;
[0030] c4) In step c), the esterification reaction temperature is -55°C to -65°C, such as -60°C or -63°C; the reaction time is 2 to 4 hours, such as 2.5 hours or 3 hours.
[0031] In one embodiment of the first aspect, the purification c5) in step c) comprises the following steps:
[0032] c51) quenching the mixed solution after the reaction in step c) with water to obtain a mixed solution containing the compound of formula I;
[0033] c52) separating the mixed solution containing the compound of formula I into layers to obtain a first organic phase and a first aqueous phase;
[0034] c53) washing the first organic phase with water and salt to obtain a second organic phase;
[0035] c54) adding phenothiazine to the second organic phase, and concentrating the second organic phase to obtain a crude product;
[0036] c55) The crude product is passed through a silica gel column to obtain the compound of formula I.
[0037] In one embodiment of the first aspect, the purification c5 further comprises at least one of the following technical features:
[0038] c531) In step c53), the salt washing is washing with a saturated NaCl solution;
[0039] c541) In step c54), the amount of phenothiazine added is 0.05-0.5 wt% of the compound of formula II, such as 0.1 wt% or 0.3 wt%;
[0040] c542) In step c54), the concentration temperature is 25°C and the pressure is 0.08MP.
[0041] c551) In step c55), the eluent for the silica gel column is a mixture of petroleum ether and ethyl acetate, and the volume ratio of petroleum ether:ethyl acetate is (4-2):1.
[0042] Compared with the prior art, the beneficial effects of the present invention are: the preparation method controls the temperature to avoid the impurities from becoming larger due to excessively high temperature, reduces the impact of materials, and obtains a product with high yield and high purity. BRIEF DESCRIPTION OF THE DRAWINGS
[0043] Figure 1 This is the GC spectrum of the product obtained in Example 1.
[0044] Figure 2 The NMR spectrum of the product obtained in Example 1 is shown in FIG. DETAILED DESCRIPTION
[0045] Unless otherwise indicated, implied from the context, or customary in the prior art, all parts and percentages in this application are based on weight, and the test and characterization methods used are all current as of the filing date of this application. Where applicable, the contents of any patent, patent application or publication referred to in this application are fully incorporated herein by reference, and their equivalent patent families are also incorporated by reference, especially the definitions of synthesis techniques, product and processing designs, polymers, comonomers, initiators or catalysts disclosed in these documents in the art. If the definition of a specific term disclosed in the prior art is inconsistent with any definition provided in this application, the definition of the term provided in this application shall prevail.
[0046] Numerical ranges in this application are approximate values, so unless otherwise specified, they may include values outside the range. Numerical ranges include all values from the lower limit to the upper limit increased by 1 unit, provided that there is an interval of at least 2 units between any lower value and any higher value. For example, if the recorded component, physical or other properties (such as molecular weight, etc.) are 100 to 1000, it means that all single values are clearly listed, such as 100, 101, 102, etc., and all sub-ranges, such as 100 to 166, 155 to 170, 198 to 200, etc. For a range containing a value less than 1 or containing a fraction greater than 1 (such as 1.1, 1.5, etc.), 1 unit is appropriately regarded as 0.0001, 0.001, 0.01 or 0.1. For a range containing a single digit less than 10 (such as 1 to 5), 1 unit is usually regarded as 0.1. These are only specific examples of what is intended to be expressed, and all possible combinations of values between the lowest and highest values listed are considered to be clearly recorded in this application. It should also be noted that the terms "first", "second", etc. in this article do not limit the order of precedence, but are only used to distinguish substances with different structures.
[0047] When used with respect to chemical compounds, unless expressly specified otherwise, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively). In addition, nouns using "a," "an," or "the" also include their plural forms unless expressly specified otherwise.
[0048] The terms "comprising", "including", "having" and their derivatives do not exclude the presence of any other components, steps or processes, and are irrelevant to whether these other components, steps or processes are disclosed in this application. To eliminate any doubt, unless explicitly stated, all compositions using the terms "comprising", "including", or "having" in this application may include any additional additives, adjuvants or compounds. On the contrary, except for those necessary for operating performance, the term "essentially consisting of..." excludes any other components, steps or processes from the scope of any description of the term below. The term "consisting of..." does not include any components, steps or processes that are not specifically described or listed. Unless explicitly stated, the term "or" refers to the listed individual members or any combination thereof.
[0049] Example
[0050] The embodiments of the present invention will be described in detail below. This embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation method and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
[0051] Example 1 1.
[0053]
[0054] Add 4-pentenoic acid (100g, 1mol) and formic acid (595g, 11mol) with a mass concentration of 85% to a four-necked bottle, heat to 50℃ and stir, control the temperature at 50-60℃ and continuously bubble in oxygen (about 4 equivalents) for reaction, the time of introduction is about 5h, sample and GC are controlled, until the residual raw material is less than 2%. Cool to room temperature, concentrate under reduced pressure to remove the solvent, and obtain an intermediate. Add 264g methanol and 8.09g concentrated hydrochloric acid (mass concentration is 36%) to the obtained intermediate, control the temperature at 20-30℃ and stir for 2h, sample and GC are controlled, until the residual intermediate is less than 1%. Concentrate under reduced pressure to remove the solvent (temperature 25-45℃, pressure 0.01-0.03MP), and after desolventization, pull the oil pump dry (oil bath 25-45℃, pressure 20-130MP), and obtain 95g of 4-hydroxymethyl-γ-butyrolactone, with a molar yield of 81.9%. 2.
[0056]
[0057] 4-Hydroxymethyl-γ-butyrolactone (400g, 3.44mol) and 2L dichloromethane were added to a 5L four-necked bottle, and the temperature was lowered to -65℃~-60℃ under nitrogen protection. Triethylamine (382.6g, 3.78mol) was added at an internal temperature of -65℃, and the temperature was controlled at -55℃~-65℃. After the addition of triethylamine, the temperature was lowered to -65℃, and methacryloyl chloride (378g, 3.62mol) was added dropwise, and the temperature was controlled at -55℃~-65℃. After the methacryloyl chloride was added dropwise, the reaction was kept warm for 3h, and a sample was taken, and the solution was quenched with water. The lower layer was taken, and the GC purity was 94%. The reaction was stopped, 1L of water was added to quench, and the solution was naturally warmed to room temperature. The reaction solution was separated into layers, and the lower organic phase was taken out and washed once with 1 L of water and once with 1 L of saturated brine. 0.6 g of phenothiazine (0.16 wt% of methacryloyl chloride) was added to the lower organic phase and desolventized (25°C, small water pump 0.08 MP) to obtain 739.7 g of crude product.
[0058] 3. Column: When the crude product is passed through the column, first use petroleum ether and ethyl acetate with a volume ratio of 6:1 to flush out impurities, using 30L, and then use petroleum ether:ethyl acetate with a volume ratio of 4:1, 3:1, and 2:1 to flush 3 times, using a total of 20L of eluent to obtain 434g of product with a GC purity of 98.9% and a molar yield of 68.5%. The GC spectrum is shown in Figure 1 , NMR spectrum see Figure 2 .
[0059] Example 2 1.
[0061]
[0062] Add 4-pentenoic acid (100g, 1mol) and formic acid (595g, 11mol) with a mass concentration of 85% to a four-necked bottle, heat to 50℃ and stir, control the temperature at 50-60℃ and continuously bubble in oxygen (about 3 equivalents) for reaction, the time of introduction is about 4h, sample and GC control, until the residual raw material is less than 2%. Cool to room temperature, reduce pressure and concentrate to remove the solvent to obtain an intermediate, add 264g methanol and 8.09g concentrated hydrochloric acid (mass concentration is 36%) to the obtained intermediate, control the temperature at 20-30℃ and stir for 1.5h. Take a sample and control in GC until the residual intermediate is less than 1%. Reduce pressure and concentrate to remove the solvent (temperature 25-45℃, pressure 0.01-0.03MP), and after desolventizing, pull the oil pump dry (oil bath 25-45℃, pressure 20-130MP), and obtain 91g of 4-hydroxymethyl-γ-butyrolactone, with a molar yield of 78.5%. 2.
[0064]
[0065] 4-Hydroxymethyl-γ-butyrolactone (400g, 3.44mol) and 2L dichloromethane were added to a 5L four-necked bottle, and the temperature was lowered to -65℃~-60℃ under nitrogen protection. Triethylamine (382.6g, 3.78mol) was added at an internal temperature of -65℃, and the temperature was controlled at -55℃~-65℃. After the triethylamine was added, the temperature was lowered to -65℃, and methacryloyl chloride (378g, 3.62mol) was added dropwise, and the temperature was controlled at -55℃~-65℃. After the methacryloyl chloride was added dropwise, the reaction was kept warm for 2h, and a sample was taken, and the solution was quenched with water. The lower layer was taken, and the GC purity was 93.5%. The reaction was stopped, 1L water was added to quench, and the solution was naturally warmed to room temperature. The reaction solution was separated into layers, and the lower organic phase was taken out and washed once with 1 L of water and once with 1 L of saturated brine. 0.6 g of phenothiazine (0.16 wt% of methacryloyl chloride) was added to the lower organic phase and desolventized (25°C, small water pump 0.08 MP) to obtain 730 g of a crude product.
[0066] 3. Column: When the crude product is passed through the column, first use petroleum ether and ethyl acetate in a volume ratio of 6:1 to flush out impurities, using 30L, and then rinse three times with petroleum ether:ethyl acetate in a volume ratio of 4:1, 3:1, and 2:1, using a total of 20L of eluent to obtain 422g of product with a GC purity of 98.2% and a molar yield of 66.6%.
[0067] Example 3 1.
[0069]
[0070] Add 4-pentenoic acid (100g, 1mol) and formic acid (595g, 11mol) with a mass concentration of 85% to a four-necked bottle, heat to 50℃ and stir, control the temperature at 50-60℃ and continuously bubble in oxygen (about 5 equivalents) for reaction, the time of introduction is about 6h, sample and GC control, until the residual raw material is less than 2%. Cool to room temperature, reduce pressure and concentrate to remove the solvent to obtain an intermediate, add 264g methanol and 8.09g concentrated hydrochloric acid (mass concentration is 36%) to the intermediate, control the temperature at 20-30℃ and stir for 3h. Take a sample and control in GC, until the residual intermediate is less than 1%. Reduce pressure and concentrate to remove the solvent (temperature 25-45℃, pressure 0.01-0.03MP), and after desolventizing, pull the oil pump dry (oil bath 25-45℃, pressure 20-130MP), and obtain 97g of 4-hydroxymethyl-γ-butyrolactone, with a molar yield of 83.6%. 2.
[0072]
[0073] 4-Hydroxymethyl-γ-butyrolactone (400g, 3.44mol) and 2L dichloromethane were added to a 5L four-necked bottle, and the temperature was lowered to -65℃~-60℃ under nitrogen protection. Triethylamine (382.6g, 3.78mol) was added at an internal temperature of -65℃, and the temperature was controlled at -55℃~-65℃. After the addition of triethylamine, the temperature was lowered to -65℃, and methacryloyl chloride (378g, 3.62mol) was added dropwise, and the temperature was controlled at -55℃~-65℃. After the methacryloyl chloride was added dropwise, the reaction was kept warm for 4h, and a sample was taken, and the solution was quenched with water. The lower layer was taken, and the GC purity was 94.6%. The reaction was stopped, 1L of water was added to quench, and the solution was naturally warmed to room temperature. The reaction solution was separated into layers, and the lower organic phase was taken out and washed once with 1 L of water and once with 1 L of saturated brine. 0.6 g of phenothiazine (0.16 wt% of methacryloyl chloride) was added to the lower organic phase and desolventized (25°C, small water pump 0.08 MP) to obtain 744 g of crude product.
[0074] 3. Column: When the crude product is passed through the column, first use petroleum ether and ethyl acetate in a volume ratio of 6:1 to flush out impurities, using 30L, and then rinse three times with petroleum ether:ethyl acetate in a volume ratio of 4:1, 3:1, and 2:1, using a total of 20L of eluent to obtain 441g of product with a GC purity of 99.1% and a molar yield of 69.6%.
[0075] The above description of the embodiments is to facilitate those of ordinary skill in the art to understand and apply the present application. It is obvious that those familiar with the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without having to pay creative labor. Therefore, the present application is not limited to the embodiments herein, and improvements and modifications made by those skilled in the art based on the contents disclosed in the present application without departing from the scope and spirit of the present application are within the scope of the present application.
Claims
1. A method for preparing a photoresist resin monomer containing a lactone structure, characterized in that: The reaction scheme of the preparation method is as follows: Wherein, R1 and R2 are hydrogen atoms or alkyl groups respectively; The preparation method comprises the following steps: a) mixing a compound of formula IV and 85 wt% formic acid, and introducing oxygen into the mixture for a reaction at 50-60° C. for 4-6 hours to obtain an intermediate, wherein the molar ratio of the compound of formula IV to oxygen is 1:(3-5); b) adding methanol and concentrated hydrochloric acid to the intermediate obtained in step a), performing a ring-opening reaction, and concentrating the mixed solution after the reaction under reduced pressure and pumping dry to obtain a compound of formula III; c) adding the compound of formula III obtained in step b) to an organic solvent, adding an acid-binding agent under nitrogen, then dropwise adding the compound of formula II, subjecting the reaction to esterification at -55°C to -65°C for 2 to 4 hours, and purifying to obtain a compound of formula I, wherein the temperature used for adding the acid-binding agent and dropwise adding the compound of formula II is both -55°C to -65°C; The purification c5) in step c) comprises the following steps: c51) quenching the mixed solution after the reaction in step c) with water to obtain a mixed solution containing the compound of formula I; c52) separating the mixed solution containing the compound of formula I into layers to obtain a first organic phase and a first aqueous phase; c53) washing the first organic phase with water and salt to obtain a second organic phase; the salt washing is washing with a saturated NaCl solution; c54) adding phenothiazine to the second organic phase, concentrating the second organic phase to obtain a crude product; the amount of phenothiazine added is 0.05-0.5 wt% of the compound of formula II; the temperature used for the concentration is 25° C. and the pressure is 0.08 MPa; c55) the crude product is passed through a silica gel column to obtain the compound of formula I; the eluent for the silica gel column is a mixture of petroleum ether and ethyl acetate, and the volume ratio of petroleum ether:ethyl acetate is (4-2):
1.
2. The method for preparing a photoresist resin monomer containing a lactone structure according to claim 1, characterized in that: The preparation method also includes at least one of the following technical features: b1) In step b), the mass ratio of methanol to concentrated hydrochloric acid is (80-100):1; b2) in step b), the concentration of concentrated hydrochloric acid is 36wt%; b3) In step b), the ring-opening reaction is carried out at a temperature of 20 to 30° C. and for a time of 1.5 to 3 hours.
3. The method for preparing a photoresist resin monomer containing a lactone structure according to claim 1, characterized in that: The step b) further comprises at least one of the following technical features: b41) In step b), the temperature used for the reduced pressure concentration is 25-45°C and the pressure is 0.01-0.03MP; b42) In step b), the oil bath temperature of the oil pump is 25-45°C and the pressure is 20-130Pa.
4. The method for preparing a photoresist resin monomer containing a lactone structure according to claim 1, characterized in that: The preparation method also includes at least one of the following technical features: c1) In step c), the molar ratio of the compound of formula III, the acid binding agent and the compound of formula II is 1:(1-2):(1-2).