CN115819237A

CN115819237A - Preparation method of fluorine-containing photoresist resin monomer

Info

Publication number: CN115819237A
Application number: CN202211674533.9A
Authority: CN
Inventors: 傅志伟; 纪兴跃; 任万鑫; 潘新刚; 余文卿
Original assignee: Xuzhou B&c Chemical Co ltd
Current assignee: Xuzhou B&c Chemical Co ltd
Priority date: 2022-12-26
Filing date: 2022-12-26
Publication date: 2023-03-21

Abstract

The invention provides a preparation method of a fluorine-containing photoresist resin monomer. The preparation method of the fluorine-containing photoresist resin comprises the following steps: under inert conditions, the compounds of formula I-1

With compounds of the formula I-2

Carrying out esterification reaction to obtain the compound of the formula I

The preparation method of the fluorine-containing photoresist resin monomer has simple synthetic route, does not contact additional factors such as acid, alkali, water and the like which can influence the decomposition of the product in the synthetic process, and greatly simplifies the synthesis and the subsequent operation procedures; the theoretical yield can be basically achieved;the yield of the obtained product can reach more than 98 percent, and the purity can reach more than 99 percent.

Description

Preparation method of fluorine-containing photoresist resin monomer

Technical Field

The invention relates to the technical field of organic synthesis, in particular to a preparation method of a fluorine-containing photoresist resin monomer.

Background

Photoresist (Photoresist), also called Photoresist, refers to a resist etching film material whose solubility changes by the irradiation or radiation of ultraviolet light, electron beam, ion beam, X-ray, etc., and its main components are polymer resin, photoacid generator, and corresponding additive and solvent. Photoresists are classified into positive and negative according to the image they form. In the photoresist process, after the coating is exposed and developed, the exposed part is dissolved, the unexposed part is remained, and the coating material is a positive photoresist. If the exposed portions are left exposed and the unexposed portions are dissolved, the coating material is a negative photoresist. With the development of photoresists, from 365nm, 248nm, 193nm to 193nm immersion, the photoresist becomes more and more hydrophobic.

The fluorine-containing compound resin monomer has certain hydrophobicity and is widely used in 193 immersion photoresist, but because of strong electronegativity of fluorine, the monomer containing more fluorine is less stable and is easily decomposed in the reaction and post-treatment processes, so that the synthesis of high-purity fluorine-containing monomer has been difficult.

Disclosure of Invention

In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a method for producing a fluorine-containing photoresist resin with high yield and high purity.

In order to achieve the above object, the present invention provides a method for preparing a fluorine-containing photoresist resin, comprising the steps of: carrying out esterification reaction on the compound shown in the formula I-1 and the compound shown in the formula I-2 under inert gas to obtain the compound shown in the formula I, wherein the reaction route is as follows:

wherein R is ₁ Is a hydrogen atom or a methyl group, R ₂ Is perfluoroAlkyl, 1 ≦ n ≦ 4, n is a positive integer.

Further, said R ₂ Is C1-C4 perfluoroalkyl.

Further, the molar ratio of the compound of formula I-1 to the compound of formula I-2 is: 1;

further, the inert gas is selected from nitrogen or argon.

Further, the reaction temperature of the esterification reaction is 0 to 30 ℃, preferably 0 to 5 DEG C

Further, the reaction time of the esterification reaction is 2 to 20 hours, preferably 3 hours.

Further, the method also comprises the following steps: concentrating the reaction product under reduced pressure to obtain crude product, and purifying the crude product by reduced pressure distillation

Further, the reduced pressure concentration is carried out under the conditions of a common water pump, the vacuum degree of 600pa and the temperature of 35-40 ℃.

Compared with the prior art, the invention

The method has the advantages of simple synthetic route, no contact with additional factors such as acid, alkali and water which can affect the decomposition of the product in the synthetic process, great simplification of the synthesis and subsequent operation procedures, cost saving, improvement of purity and yield, achievement of the yield of the product of more than 98% and theoretical yield of more than 99%.

Drawings

FIG. 1 is a HNMR map of the product prepared in example 1;

FIG. 2 is a FNMR map of the product prepared in example 1;

FIG. 3 is a HNMR map of the product prepared in example 2;

FIG. 4 is a FNMR map of the product prepared in example 2.

Detailed Description

The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.

In the present invention, the equipment, raw materials, etc. used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.

Example 1

After nitrogen replacement, trifluoroacetic anhydride (1kg, 4.76mol) is added into a 2L reaction bottle, the temperature is reduced to 0-5 ℃, hydroxyethyl methacrylate (309.67g, 2.38mol) is dripped, the temperature is controlled to 0-5 ℃, the dripping is finished, and the stirring reaction is carried out for 3 hours under the condition of maintaining the temperature of 0-5 ℃.

After the reaction is finished, decompressing and concentrating to remove redundant trifluoroacetic anhydride and generated by-product trifluoroacetic acid to obtain crude light yellow liquid, decompressing, distilling and purifying to obtain pure colorless liquid (529g, 2.33), the yield is 98.3%, and the GC purity is 99%. The HNMR spectrum is shown in figure 1, and the FNMR spectrum is shown in figure 2.

In the reaction process, other substances such as a solvent, an acid binding agent and the like are not used, because the product is easy to damage when meeting the substances, the yield is low, the purity is poor, the substances are omitted, the cost is saved, and the purity and the yield are improved.

Example 2

Replacing nitrogen in a 1L reaction bottle, adding pentafluoropropionic anhydride (500g, 1.61mol), cooling to 0-5 ℃, dropwise adding hydroxyethyl methacrylate (104.87g, 0.81mol), controlling the temperature to 0-5 ℃, completely dropwise adding, and stirring and reacting for 3 hours at the temperature of 0-5 ℃.

After the reaction is finished, decompressing and concentrating to remove redundant pentafluoropropionic anhydride and the generated byproduct pentafluoropropionic acid to obtain crude light yellow liquid, decompressing, distilling and purifying to obtain pure colorless liquid (219g, 0.79mol), wherein the yield is 98.4 percent, and the GC purity is 99 percent. The HNMR spectrum is shown in FIG. 3, and the FNMR spectrum is shown in FIG. 4.

The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims

1. A preparation method of fluorine-containing photoresist resin monomer is characterized by comprising the following steps: carrying out esterification reaction on the compound shown in the formula I-1 and the compound shown in the formula I-2 under inert gas to obtain the compound shown in the formula I, wherein the reaction route is as follows:

wherein R is ₁ Is a hydrogen atom or a methyl group, R ₂ Is a perfluoroalkyl group, 1 ≦ n ≦ 4, n is a positive integer.

2. The method for producing a fluorine-containing resist resin monomer according to claim 1, wherein R is R ₂ Is C1-C4 perfluoroalkyl.

3. The method for producing a fluorine-containing resist resin monomer according to claim 1, wherein the molar ratio of the compound of formula I-1 to the compound of formula I-2 is 1 to 1.

4. The method of preparing a fluorine-containing photoresist resin monomer according to claim 1, wherein the inert gas is selected from nitrogen or argon.

5. The method for producing a fluorine-containing resist resin monomer according to claim 1, wherein the temperature of the esterification reaction is 0 to 30 ℃.

6. The method for preparing a fluorine-containing photoresist resin monomer according to claim 1, wherein the time of the esterification reaction is 2 to 20 hours.

7. The method for preparing a fluorine-containing photoresist resin monomer according to claim 1, further comprising the steps of: and concentrating the reaction product under reduced pressure to obtain a crude product, and carrying out reduced pressure distillation and purification on the crude product.

8. The method for producing a fluorine-containing resist resin monomer according to claim 7, wherein the concentration under reduced pressure is carried out under conditions of a normal water pump, a degree of vacuum of 600pa, and a temperature of 35 to 40 ℃.