CN114276317A - Preparation method of photoresist resin monomer containing lactone structure - Google Patents

Abstract

The invention relates to a preparation method of a photoresist resin monomer containing a lactone structure, which comprises the following synthetic route:

wherein R is₁And R₂Are each a hydrogen atom or an alkyl group; the preparation method specifically comprises the following steps: a) mixing and heating the compound IV and sulfur powder, dripping liquid bromine under the heating condition, and carrying out substitution reaction to obtain a mixture containing a compound III; b) adding dichloromethane and ice water into the mixture containing the compound III obtained in the step a) for extraction, then washing an organic phase with water, then washing with alkali, adjusting the pH value of the organic phase to 6-7, concentrating and distilling to obtain a compound III; c) mixing the compound III, the compound II and a polymerization inhibitor obtained in the step b) with dichloromethane, dropwise adding triethylamine, performing esterification reaction, and purifying a mixed solution after the reaction to obtain a photoresist resin monomer I containing a lactone structure. The preparation method of the invention obtainsThe product has high yield, high purity and less impurities.

Description

Preparation method of photoresist resin monomer containing lactone structure

Technical Field

The invention relates to the technical field of ArF photoresist, in particular to a preparation method of a photoresist resin monomer containing a lactone structure.

Background

The 193nm photoresist is basically a chemically amplified resist, which is a photoresist based on the principle of chemical amplification and mainly comprises a polymer resin, a photoacid generator, and corresponding additives (alkaline additives, dissolution inhibitors, etc.) and a solvent. Among them, the polymer resin is formed by copolymerization between resin monomers having different side chain structures, which are key components for imparting desired functions to the polymer resin, and usually provides the polymer resin with a polar group and an acid-sensitive group. 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 host resin. The acid sensitive group can be separated from the side chain under the action of a photoacid generator, so that the resin is converted from insoluble to alkali-soluble, and the solubility contrast of the exposed region and the unexposed region is realized. Wherein the polar group comprises hydroxyl, carboxyl, lactone group (such as 1, 4-butyrolactone, delta-cyclopentanolide, beta-dimethyl-gamma-butyrolactone), etc.

The resin system of the lactone is a resin polymer widely applied to 193nm photoresist, but the resin monomer of the lactone prepared by the prior art is easy to polymerize and has low purity.

Disclosure of Invention

The present invention is directed to overcoming the above-mentioned drawbacks of the prior art and providing a method for preparing a photoresist resin monomer containing a lactone structure.

In order to achieve the object of the present invention, the present application provides the following technical solutions.

In a first aspect, the present application provides a method for preparing a lactone structure-containing photoresist resin monomer, the method comprising the following synthetic route:

wherein R is₁And R₂Are each a hydrogen atom or an alkyl group;

preferably, R₁And R₂Each is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; such as R₁Is a hydrogen atom, a methyl or ethyl group, R₂Is a hydrogen atom, a methyl group or an ethyl group;

the preparation method specifically comprises the following steps:

a) mixing and heating the compound IV and sulfur powder, dripping liquid bromine under the heating condition, and carrying out substitution reaction to obtain a mixture containing a compound III;

b) adding dichloromethane and ice water into the mixture containing the compound III obtained in the step a) for extraction, then washing an organic phase with water, then washing with alkali, adjusting the pH value of the organic phase to 6-7, concentrating and distilling to obtain a compound III;

c) mixing the compound III, the compound II and a polymerization inhibitor obtained in the step b) with dichloromethane, dropwise adding triethylamine, performing esterification reaction, and purifying a mixed solution after the reaction to obtain the lactone structure-containing photoresist resin monomer I.

In an embodiment of the first aspect, in step a), at least one of the following technical features is further included:

a1) the molar ratio of the compound IV to the liquid bromine to the sulfur powder is 1: (1-3): (0.01 to 0.2) as defined in 1: 1: 0.1 or 1: 1.5: 0.1 or 1: 2: 0.05 or 1: 3: 0.1 or 1: 3: 0.2;

a2) the heating temperature is 80-90 ℃, such as 80 ℃ or 85 ℃ or 90 ℃;

a3) the time for dripping the liquid bromine is 2 h-4 h, such as 2h or 4 h;

a4) the temperature of the heat preservation reaction is 75-85 ℃, such as 75 ℃ or 80 ℃, and the time of the heat preservation reaction is 2-4 h, such as 2h or 3 h.

In an embodiment of the first aspect, in step b), at least one of the following technical features is further included:

b1) firstly introducing inert gas into the mixture containing the compound III obtained in the step a);

b2) in step b), the alkali washing is a saturated sodium bicarbonate solution washing;

b3) the distillation is oil pump distillation, and fractions with the top temperature of 68-74 ℃ are collected, such as 70 ℃ or 72 ℃;

further, the oil temperature for oil pump distillation is 80-150 ℃, such as 90 ℃ or 100 ℃; the distillation time is 5-20 h, such as 6h, 10h or 15h, and the vacuum degree is 30-50 Pa, such as 35Pa, 40Pa or 45 Pa.

In an embodiment of the first aspect, at least one of the following technical features is further included:

b11) in the step b1), the inert gas is introduced for 0.5 to 2 hours, such as 1 hour or 1.5 hours;

b12) in step b1), the inert gas is nitrogen.

In an embodiment of the first aspect, step c) further includes at least one of the following technical features:

c1) the molar ratio of the compound III to the compound II to the triethylamine is (1-2): (1-3); the method comprises the following steps of 1: 2: 2.6 or 1: 2: 3 or 1: 1: 2 or 1: 1.5: 2;

c2) the temperature for dripping triethylamine is 10-25 ℃, such as 12 ℃,15 ℃ or 20 ℃, and the time for dripping is 1.5-4.5 h; such as 2h or 3h or 4 h;

c3) the temperature of the heat preservation reaction is 28-35 ℃, such as 30 ℃ or 32 ℃; the time of the heat preservation reaction is 5-6 h, such as 5.5 h.

c4) The polymerization inhibitor is selected from at least one of 2, 6-di-tert-butylphenol, p-tert-butylcatechol, hydroquinone and bisphenol A.

In one embodiment of the first aspect, the purification in step c) comprises the steps of:

d1) carrying out suction filtration on the reaction liquid obtained in the step c) after the heat preservation reaction to obtain a first filtrate and a first filter cake;

d2) decompressing and concentrating the first filtrate obtained in the step d1), adding methyl tert-butyl ether for pulping, and performing suction filtration to obtain a second filtrate and a second filter cake;

d3) adding water into the second filter cake obtained in the step d2), stirring, standing for layering to obtain a first water phase, and extracting the first water phase by using methyl tert-butyl ether to obtain a first organic phase;

d4) combining the second filtrate in d2) and the first organic phase extracted in d3), and obtaining a crude product through salt washing, drying, filtering and concentrating;

d5) the crude product is subjected to distillation.

In an embodiment of the first aspect, step d4) further includes at least one of the following technical features:

d41) in step d4), the salt wash is a saturated sodium chloride solution wash;

d42) in step d4), the drying agent used for the drying is anhydrous sodium sulfate or anhydrous magnesium sulfate.

In one embodiment of the first aspect, step d5) further includes the following features:

d51) in the step d5), the distillation is reduced pressure distillation, and the fraction with the temperature of 78-84 ℃ is collected, such as 79 ℃ or 80 ℃;

further, the external temperature of the reduced pressure distillation is 110-135 ℃, such as 120 ℃ or 130 ℃; the degree of vacuum was 1 mmHg.

Compared with the prior art, the invention has the beneficial effects that:

in the preparation method, the pH value is strictly controlled to be 6-7 in the step b), so that the content of the compound III can reach more than 98%, and the yield is more than 85%. Then further reaction and purification are carried out, and polymerization is reduced by controlling the distillation vacuum degree to 1mmHg, so that the photoresist resin with the lactone structure has high single yield, high purity and less impurities.

Drawings

FIG. 1 is a GC spectrum of α -bromo- γ -butyrolactone in example 1.

FIG. 2 is a GC spectrum of the product prepared in example 1.

Detailed Description

Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are incorporated herein by reference in their entirety and their equivalent family patents are also incorporated by reference, especially as they disclose definitions relating to synthetic techniques, products and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.

The numerical ranges in this application are approximations, and thus may include values outside of the ranges unless otherwise specified. A numerical range includes all numbers from the lower value to the upper value, in increments of 1 unit, provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if a component, physical or other property (e.g., molecular weight, etc.) is recited as 100 to 1000, it is intended that all individual values, e.g., 100, 101,102, etc., and all subranges, e.g., 100 to 166,155 to 170,198 to 200, etc., are explicitly recited. For ranges containing a numerical value less than 1 or containing a fraction greater than 1 (e.g., 1.1, 1.5, etc.), then 1 unit is considered appropriate to be 0.0001, 0.001, 0.01, or 0.1. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is typically considered 0.1. These are merely specific examples of what is intended to be expressed and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application. It should also be noted that the terms "first," "second," and the like herein do not define a sequential order, but merely distinguish between different structures.

When used with respect to chemical compounds, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively) unless expressly specified otherwise. In addition, unless explicitly stated otherwise, the use of the terms "a", "an" or "the" are intended to include the plural forms thereof.

The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not intended to exclude the presence of other elements, steps or procedures not expressly disclosed herein. To the extent that any doubt is eliminated, all compositions herein containing, including, or having the term "comprise" may contain any additional additive, adjuvant, or compound, unless expressly stated otherwise. Rather, the term "consisting essentially of … …" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, except those necessary for performance. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.

Examples

The following will describe in detail the embodiments of the present invention, which are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and the specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.

Example 1

1、

Adding 1, 4-butyrolactone (100g, 1.16mol) and sulfur powder (3.71g, 0.116mol) into a 1L four-mouth bottle, starting stirring, heating to 80 +/-5 ℃, stopping heating, starting to dropwise add liquid bromine (186g, 1.16mol), controlling the temperature to be 85 +/-5 ℃, starting heating after 2h of dropwise addition, keeping the temperature at 80 ℃ for reaction, starting sampling after 2h, and detecting that the raw materials are less than 5% by GC.

2. Introducing nitrogen into the reaction solution for 1h, stopping heating, cooling to 30 ℃, adding dichloromethane (450g) into a reaction bottle, stirring for 10min, adding 150g of ice/250 g of water, stirring for 30min, separating liquid, washing with water for the first time (250g), combining the water phases, and extracting with dichloromethane (300 g); the organic phases were combined and the pH of the organic phase was adjusted with a saturated solution of sodium bicarbonate (ca. 2L) to bring the pH of the aqueous layer to 7; separating, and washing the organic phase once (250g) for the second time; the combined aqueous sodium bicarbonate phase and the second aqueous wash phase were extracted with dichloromethane (250 g); the organic phase was dried over anhydrous sodium sulfate and concentrated to give 190g of crude product. And (3) performing oil pump distillation on the crude product, wherein the oil temperature of the oil pump is about 90 ℃, the vacuum degree is 30-50 Pa, 165g of the fraction alpha-bromo-gamma-butyrolactone with the top temperature of 70 ℃ is collected, the yield is 86.1%, the purity is 99.1%, and a GC spectrum is shown in figure 1.

3、

Adding dichloromethane (600g), alpha-bromo-gamma-butyrolactone (100g, 0.606mol), methacrylic acid (104.36g, 1.212mol) and 2, 6-di-tert-butylphenol (0.5g) into a 2L four-mouth bottle, cooling to below 15 ℃, stirring, dropwise adding triethylamine (159.47g, 1.576mol), controlling the temperature at 10-25 ℃, and completing dropwise addition within about 2 hours; and (3) carrying out heat preservation reaction for 5-6 hours at the temperature of 28-35 ℃, and detecting complete reaction of the raw materials by GC.

Directly filtering the reaction solution, washing a filter cake with dichloromethane, and combining organic phases; concentrating under reduced pressure, adding methyl tert-butyl ether (MTBE), stirring for 30min, vacuum filtering to remove salt and polymer, washing filter cake with MTBE, adding water, stirring for 30min, standing for layering, extracting water phase with MTBE, and mixing MTBE phases; the mixture was washed once with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to dryness to give 67g of crude product. And (3) carrying out reduced pressure distillation on the crude product for 2 times, wherein the vacuum degree is about 1mmHg, the external temperature is 110-135 ℃, 52g of fraction at 78-84 ℃ is collected, the yield is 50.42%, the purity is 99.6%, and a GC spectrogram is shown in figure 2.

Example 2

1、

Adding 1, 4-butyrolactone (100g, 1.16mol) and sulfur powder (3.71g, 0.116mol) into a 1L four-mouth bottle, starting stirring, heating to 80 +/-5 ℃, and stopping heating; and (3) beginning to dropwise add liquid bromine (186g, 1.16mol), controlling the temperature to be 85 +/-5 ℃, starting heating after finishing dropwise adding for 3 hours, keeping the temperature at 75 ℃ for reaction, beginning to sample after 2 hours, and detecting the raw material to be less than 5% by GC.

2. Introducing nitrogen into the reaction liquid for 0.5h, stopping heating, cooling to 30 ℃, adding dichloromethane (450g) into a reaction bottle, stirring for 10min, adding 150g of ice/250 g of water, stirring for 30min, separating liquid, washing with water for the first time (250g), and extracting the combined water phase with dichloromethane (300 g); the organic phases were combined and the pH of the organic phase was adjusted with a saturated solution of sodium bicarbonate (ca. 1.5L) to bring the pH of the aqueous layer to 6; separating, washing the organic phase once with water (250g), combining the sodium bicarbonate water phase and the second water-washed water phase, and extracting with dichloromethane (250 g); the organic phase was dried over anhydrous sodium sulfate and concentrated to give 187g of crude product. And (3) performing oil pump distillation on the crude product, wherein the oil temperature of the oil pump is about 90 ℃, the vacuum degree is 30-50 Pa, 163g of fraction alpha-bromo-gamma-butyrolactone with the top temperature of 70 ℃ is collected, the yield is 85.2%, and the GC purity is 99.2%.

3、

Adding dichloromethane (600g), alpha-bromo-gamma-butyrolactone (100g, 0.606mol), methacrylic acid (104.36g, 1.212mol) and p-tert-butylcatechol (0.5g) into a 2L four-mouth bottle, cooling to below 15 ℃, stirring, dropwise adding triethylamine (159.47g, 1.576mol), controlling the temperature to be 10-25 ℃, completing dropwise addition within about 1.5 hours, carrying out heat preservation reaction for 5-6 hours at 28-35 ℃, and detecting by GC that the raw materials are completely reacted.

Directly filtering the reaction solution, washing a filter cake with dichloromethane, and combining organic phases; concentrating under reduced pressure, adding MTBE, stirring for 30 minutes, performing suction filtration to remove salt and polymers, washing a filter cake with MTBE, adding water, stirring for 30 minutes, standing for layering, extracting a water phase with MTBE, and combining MTBE phases; the mixture was washed once with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to dryness to obtain 70g of crude product. And carrying out reduced pressure distillation on the crude product for 2 times, wherein the vacuum degree is about 1mmHg, the external temperature is 110-135 ℃, 55g of fraction at 78-84 ℃ is collected, the yield is 53.3%, and the GC purity is 99.6%.

Example 3

1、

Adding 1, 4-butyrolactone (100g, 1.16mol) and sulfur powder (3.71g, 0.116mol) into a 1L four-mouth bottle, starting stirring, heating to 80 +/-5 ℃, stopping heating, starting dropwise adding liquid bromine (278g, 1.74mol), controlling the temperature to be 85 +/-5 ℃, starting heating after 4h of dropwise adding is finished, keeping the temperature at 85 ℃ for reaction, starting sampling after 2h, and detecting that the raw materials are less than 5% by GC.

2. Introducing nitrogen into the reaction liquid for 2 hours, stopping heating, cooling to 30 ℃, adding dichloromethane (450g) into a reaction bottle, stirring for 10min, adding 150g of ice/250 g of water, stirring for 30min, separating liquid, washing with water for the first time (250g), combining the water phases, and extracting with dichloromethane (300 g); the organic phases were combined and the pH of the organic phase was adjusted with a saturated solution of sodium bicarbonate (ca. 2L) to bring the pH of the aqueous layer to 7; separating, washing the organic phase once with water for the second time (250g), and extracting the combined aqueous phase of sodium bicarbonate and the aqueous phase of the second water washing with dichloromethane (250 g); the organic phase was dried over anhydrous sodium sulfate and concentrated to give 193g of crude product. And (3) performing oil pump distillation on the crude product, wherein the oil temperature of the oil pump is about 90 ℃, the vacuum degree is 30-50 Pa, and 169g of fraction alpha-bromo-gamma-butyrolactone with the top temperature of 70 ℃ is collected, the yield is 88.2%, and the GC purity is 99.1%.

3、

Adding dichloromethane (600g), alpha-bromo-gamma-butyrolactone (100g, 0.606mol), methacrylic acid (1043.36g, 1.212mol) and hydroquinone (0.5g) into a 2L four-mouth bottle, cooling to below 15 ℃, stirring, dropwise adding triethylamine (159.47g, 1.576mol), controlling the temperature to be 10-25 ℃, and completing dropwise addition within about 4.5 hours; and (3) carrying out heat preservation reaction for 5-6 hours at the temperature of 28-35 ℃, and detecting complete reaction of the raw materials by GC.

Directly filtering the reaction solution, washing a filter cake with dichloromethane, combining organic phases, concentrating under reduced pressure, adding MTBE, stirring for 30 minutes, removing salts and polymers by suction filtration, washing the filter cake with MTBE, adding water, stirring for 30 minutes, standing for layering, extracting a water phase with MTBE, and combining MTBE phases; the mixture was washed once with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to dryness to give 69.5g of crude product. And carrying out reduced pressure distillation on the crude product for 2 times, wherein the vacuum degree is about 1mmHg, the external temperature is 110-135 ℃, 54g of fraction at 78-84 ℃ is collected, the yield is 52.4%, and the GC purity is 99.5%.

Example 4

1、

Adding 1, 4-butyrolactone (100g, 1.16mol) and sulfur powder (3.71g, 0.116mol) into a 1L four-mouth bottle, starting stirring, heating to 80 +/-5 ℃, stopping heating, starting to dropwise add liquid bromine (186g, 1.16mol), controlling the temperature to be 85 +/-5 ℃, starting heating after 2h of dropwise addition, keeping the temperature at 80 ℃ for reaction, starting sampling after 2h, and detecting that the raw materials are less than 5% by GC.

2. Introducing nitrogen into the reaction solution for 1h, stopping heating, cooling to 30 ℃, adding dichloromethane (450g) into a reaction bottle, stirring for 10min, adding 150g of ice/250 g of water, stirring for 30min, separating liquid, washing with water for the first time (250g), combining the water phases, and extracting with dichloromethane (300 g); the organic phases were combined and the pH of the organic phase was adjusted with a saturated solution of sodium bicarbonate (ca. 2L) to bring the pH of the aqueous layer to 7; separating, washing the organic phase once with water for the second time (250g), and extracting the combined aqueous phase of sodium bicarbonate and the aqueous phase of the second water washing with dichloromethane (250 g); the organic phase was dried over anhydrous sodium sulfate and concentrated to give 190g of crude product. And (3) performing oil pump distillation on the crude product, wherein the oil temperature of the oil pump is about 90 ℃, the vacuum degree is 30-50 Pa, collecting 165g of fraction alpha-bromo-gamma-butyrolactone with the top temperature of 70 ℃, the yield is 86.1%, and the GC purity is 99.1%.

3、

Adding dichloromethane (600g), alpha-bromo-gamma-butyrolactone (100g, 0.606mol), acrylic acid (87.34g, 1.212mol) and bisphenol A (0.5g) into a 2L four-mouth bottle, cooling to below 15 ℃, stirring, dropwise adding triethylamine (159.47g, 1.576mol), controlling the temperature to be 10-25 ℃, completing dropwise addition within about 2 hours, keeping the temperature at 28-35 ℃, reacting for 5-6 hours, and detecting by GC that the raw materials are completely reacted.

Directly filtering the reaction solution, washing a filter cake with dichloromethane, combining organic phases, concentrating under reduced pressure, adding MTBE, stirring for 30 minutes, removing salts and polymers by suction filtration, washing the filter cake with MTBE, adding water, stirring for 30 minutes, standing for layering, extracting a water phase with MTBE, and combining MTBE phases; the mixture was washed once with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to dryness to give 61g of crude product. And carrying out reduced pressure distillation on the crude product for 2 times, wherein the vacuum degree is about 1mmHg, the external temperature is 110-135 ℃, 49.5g of fraction at 78-84 ℃ is collected, the yield is 52.3%, and the GC purity is 99.7%.

Comparative example 1

1、

Adding 1, 4-butyrolactone (100g, 1.16mol) and sulfur powder (3.71g, 0.116mol) into a 1L four-mouth bottle, starting stirring, heating to 80 +/-5 ℃, stopping heating, starting to dropwise add liquid bromine (186g, 1.16mol), controlling the temperature to be 85 +/-5 ℃, starting heating after finishing dropwise adding for 2h, keeping the temperature at 80 ℃ for reaction, starting sampling after 2h, and detecting the raw materials to be less than 5% by GC.

2. Introducing nitrogen into the reaction liquid for 1h, stopping heating, cooling to 30 ℃, adding dichloromethane (450g) into a reaction bottle, stirring for 10min, adding 150g of ice/250 g of water, stirring for 30min, separating liquid, washing with water for the first time (250g), extracting the combined aqueous phase with dichloromethane (300g), combining the organic phases, drying and concentrating the organic phase with anhydrous sodium sulfate to obtain 145g of crude product. And (3) performing oil pump distillation on the crude product, wherein the oil temperature of the oil pump is about 90 ℃, the vacuum degree is 30-50 Pa, collecting 109g of fraction alpha-bromo-gamma-butyrolactone with the top temperature of 70 ℃, the yield is 56.9%, and the purity is 91%.

Saturated sodium bicarbonate is not added into the organic phase containing the alpha-bromo-gamma-butyrolactone to adjust the pH value until the pH value of the water layer is 6-7, so that the yield of the product alpha-bromo-gamma-butyrolactone is greatly reduced.

3、

Adding dichloromethane (600g), alpha-bromo-gamma-butyrolactone (100g, 0.606mol), methacrylic acid (104.36g, 1.212mol) and 2, 6-di-tert-butylphenol (0.5g) into a 2L four-mouth bottle, cooling to below 15 ℃, stirring, dropwise adding triethylamine (159.47g, 1.576mol), controlling the temperature to be 10-25 ℃, completing dropwise addition within about 2 hours, carrying out heat preservation reaction at 28-35 ℃ for 5-6 hours, and detecting complete reaction of raw materials by GC.

Directly filtering the reaction solution, washing a filter cake with dichloromethane, and combining organic phases; concentrating under reduced pressure, adding MTBE, stirring for 30 minutes, performing suction filtration to remove salt and polymers, washing a filter cake with MTBE, adding water, stirring for 30 minutes, standing for layering, extracting a water phase with MTBE, and combining MTBE phases; the mixture was washed once with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to dryness to give 67g of crude product. And carrying out reduced pressure distillation on the crude product for 2 times, wherein the vacuum degree is about 10mmHg, the external temperature is 110-135 ℃, 43.3g of fraction at 78-84 ℃ is collected, the yield is 42.0%, and the GC purity is 91.1%.

The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.

Claims (8)

1. A preparation method of a photoresist resin monomer containing a lactone structure is characterized by comprising the following synthetic route:

wherein R is₁And R₂Are each a hydrogen atom or an alkyl group;

the preparation method specifically comprises the following steps:

a) mixing and heating the compound IV and sulfur powder, dripping liquid bromine under the heating condition, and carrying out substitution reaction to obtain a mixture containing a compound III;

b) adding dichloromethane and ice water into the mixture containing the compound III obtained in the step a) for extraction, then washing an organic phase with water, then washing with alkali, adjusting the pH value of the organic phase to 6-7, concentrating and distilling to obtain a compound III;

c) mixing the compound III, the compound II and a polymerization inhibitor obtained in the step b) with dichloromethane, dropwise adding triethylamine, performing esterification reaction, and purifying a mixed solution after the reaction to obtain a photoresist resin monomer I containing a lactone structure.

2. The method for preparing a lactone structure-containing photoresist resin monomer of claim 1, further comprising at least one of the following technical features in step a):

a1) the molar ratio of the compound IV to the liquid bromine to the sulfur powder is 1: (1-3): (0.01 to 0.2);

a2) the heating temperature is 80-90 ℃;

a3) the time for dripping the liquid bromine is 2-4 h;

a4) the temperature of the substitution reaction is 75-85 ℃, and the time is 2-4 h.

3. The method for preparing a lactone structure-containing photoresist resin monomer of claim 1, further comprising at least one of the following technical features in step b):

b1) firstly introducing inert gas into the mixture containing the compound III obtained in the step a);

b2) in step b), the alkali washing is a saturated sodium bicarbonate solution washing;

b3) the distillation is oil pump distillation, and fractions with the top temperature of 68-74 ℃ are collected.

4. The method for preparing a lactone structure-containing photoresist resin monomer of claim 3, further comprising at least one of the following technical features:

b11) in the step b1), the inert gas is introduced for 0.5-2 h;

b12) in step b1), the inert gas is nitrogen.

5. The method for preparing a lactone structure-containing photoresist resin monomer of claim 1, wherein step c) further comprises at least one of the following technical features:

c1) the mol ratio of the compound III to the compound II to the triethylamine is 1: (1-2): (1-3);

c2) the temperature for dripping triethylamine is 10-25 ℃, and the time for dripping is 1.5-4.5 h;

c3) the temperature of the esterification reaction is 28-35 ℃, and the time is 5-6 h.

c4) The polymerization inhibitor is selected from at least one of 2, 6-di-tert-butylphenol, p-tert-butylcatechol, hydroquinone and bisphenol A.

6. The method for preparing a lactone structure-containing photoresist resin monomer of claim 1, wherein the purification in step c) comprises the steps of:

d1) carrying out suction filtration on the reaction liquid obtained in the esterification reaction in the step c) to obtain a first filtrate and a first filter cake;

d2) decompressing and concentrating the first filtrate obtained in the step d1), adding methyl tert-butyl ether for pulping, and performing suction filtration to obtain a second filtrate and a second filter cake;

d3) adding water into the second filter cake obtained in the step d2), stirring, standing for layering to obtain a first water phase, and extracting the first water phase by using methyl tert-butyl ether to obtain a first organic phase;

d4) combining the second filtrate in d2) and the first organic phase extracted in d3), and obtaining a crude product through salt washing, drying, filtering and concentrating;

d5) the crude product is subjected to distillation.

7. The method for preparing a lactone structure-containing photoresist resin monomer of claim 6, wherein step d4) further comprises at least one of the following technical features:

d41) in step d4), the salt wash is a saturated sodium chloride solution wash;

d42) in step d4), the drying agent used for the drying is anhydrous sodium sulfate or anhydrous magnesium sulfate.

8. The method for preparing a lactone structure-containing photoresist resin monomer of claim 6, wherein step d5) further comprises the following features:

d51) in the step d5), the distillation is vacuum distillation, and the fraction with the temperature of 78-84 ℃ is collected.

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