CN118221123A - Thiol-and 4-methylaminopyridine difunctional group-containing modified silica gel base material and application thereof in preparation of photoresist resin - Google Patents

Abstract

The invention discloses a modified silica gel base material containing mercapto and 4-methylaminopyridine difunctional groups, a preparation method thereof and application thereof in the aspects of resin catalytic synthesis, acid-base residual impurity removal and metal ion impurity removal for 248nm photoresist. The invention is suitable for the technical field of synthesis and purification of resin electronic chemicals for semiconductor photoresist. The novel difunctional group-containing modified silica gel material can be used for catalytic synthesis and purification of semiconductors and display electronic chemicals, and is particularly suitable for the method for catalytic synthesis and purification of metal ion impurities of a type of resin for semiconductor chemical amplification type photoresist, and has wide application prospects.

Description

Thiol-and 4-methylaminopyridine difunctional group-containing modified silica gel base material and application thereof in preparation of photoresist resin

Technical Field

The invention belongs to the technical field of macromolecules, and particularly relates to a modified silica gel base material containing mercapto and 4-methylaminopyridine difunctional groups and application thereof in preparation of photoresist resin.

Background

In semiconductor wafer lithography, photoresist is one of the key materials. Photoresist Photoresist, also called photoresist, refers to a resist lithographic thin film material whose solubility is changed by irradiation or radiation of ultraviolet light, electron beam, ion beam, X-ray, etc., and is a key material for integrated circuit fabrication.

The resist for semiconductor ICs is classified into g-line (wavelength 436 nm), i-line (wavelength 365 nm), krF (wavelength 248 nm), arF (dry wavelength 193 nm), EUV (wavelength 13.5 nm). As the ultraviolet wavelength for lithography becomes shorter, the resolution becomes higher and higher. In the progress of finer semiconductor patterns, the requirements for impurities contained in materials such as photoresist have tended to be strict. The difficulty of photoresist preparation, except formulation performance, is mainly that the components constituting the photoresist: the quality of the resin, initiator, monomer, solvent, other additives, etc., wherein the most important key component is the resin component, directly determines the performance quality of the photoresist composition.

The quality requirement index of the resin component for the photoresist for semiconductors is high. Especially, the requirements on impurities (organic impurities, various foreign matters, metal ions and the like) are very high, and the impurities reach the standards. Metal impurities have a negative impact on semiconductor fabrication, and therefore the amount of gold impurities in photoresist materials that directly contact the wafer must be controlled to very low levels: if the metal impurities contained in the photoresist are higher, the risk that the metal impurities are finally remained on the surface of the semiconductor substrate is greatly increased, and the electrical characteristics of the semiconductor are finally damaged, so that the yield of chip products is reduced, and the cost is greatly increased. The synthetic method and the purification method are found out by fumbling and experiments aiming at photoresist component materials with different structures, and impurities such as foreign matters, metals and the like are removed. In summary, for various photoresists and other materials such as insulating films and antireflection layers used in the above fine lithography, it is necessary to control the content of various organic impurities, metal ion impurities, and the like contained therein to an extremely minute level. Thus, the photoresist and its upstream resins and intermediates all require stringent control of the metal impurity levels.

Chemical amplification type photoresists (CHEMISTRY AMPLIFICATIONPHOTORESIST) are often used in photolithography processes for high resolution I-lines and KrF and higher, i.e., the dissociation of acid sensitive groups in the resin is catalyzed by the principle that photoacid generators (photo acid generator, PAG for short) in the photoresist generate protons upon contact with photons in the exposed areas, thereby creating a distinction between solubility in the developer and patterning.

The mechanism of the chemical amplification type photoresist during the photoetching operation is that the chemical bond in the resin molecule in the positive photoresist is broken to promote quick dissolution after being irradiated by the micro photoacid generator in the photoresist formula system under the ultraviolet light with specific wavelength. Base resins of various organic polymers such as o (or m) cresol-formaldehyde resins, polyacrylic acid and its derivatives, polyhydroxystyrene and its copolymers are often used as the resin component of chemically amplified resists.

According to the use principle of the chemical amplification type photoresist (CHEMISTRY AMPLIFICATION PHOTORESIST), trace acidic substance impurities or alkaline substance impurities remained in the photoresist component can interfere with the normal working mechanism of the photoacid generator, so that the normal exposure-development process cannot be carried out, and the quality guarantee period of the photoresist can be reduced. The polyhydroxystyrene resin used in the photoresist is usually synthesized by polymerizing monomers such as 1-tert-butoxystyrene and P- (1-ethoxyethoxy) styrene; 2. the product synthesized in the previous step is deprotected, and the catalyst can be hydrochloric acid, sulfuric acid and the like; 3. partial protection of polyhydroxystyrene, such as base-catalyzed t-butoxycarbonyl protection, or Lewis acid-catalyzed addition of vinyl ethers. It is clear that the use of an acid catalyst is difficult to avoid in the synthesis of polyhydroxystyrene resins required for I-line and KrF line, and the problem of removal thereof is also a serious problem in the quality control of resins.

The method for removing the acid-base residue and metal ion impurities in the photoresist material is always focused on by industrial scientific researchers, and in the known purification and impurity removal method, specific acid-base residue impurities, metal ion impurities and the like are mainly carried out in different methods and different working procedures.

Reported methods can be broadly divided into the following categories: 1. ultra-pure water washing, including links of extraction, resin washing and the like, is often repeated and repeated water washing to achieve the aim due to extremely high requirements on impurity residues in the semiconductor industry, and needs additional drying and moisture removal; 2. purifying anion and cation exchange resins, and according to different impurity removal properties and types, carrying out complicated pretreatment on the anion and cation exchange resins so as not to introduce other impurities to pollute products in use; 3. other common adsorbents such as activated carbon, silica gel and the like are used for purifying impurities such as metal and the like in resin solutions, the effect of different adsorbent schemes depends on parameters such as the type, structure, pore size and the like of the adsorbent, the adsorption capacity of different metal impurities and organic impurities is greatly different, and the purification of specific impurities in photoresist resins cannot be well matched.

The silica gel particles are commonly used in industry, have a large number of pore canal structures, large specific surface area and good chemical and mechanical stability, are often used as carriers of adsorption materials, and can purify and adsorb color impurities, metal ion impurities and the like. The amino functional group (-NH 2, -NH-) has stronger adsorption effect on specific groups, metal ions and the like, so that silica gel is used as a matrix carrier, and an organic matter containing the amino functional group is used as a modifier, and the prepared amino modified silica gel material has excellent chemical stability and mechanical stability and larger adsorption capacity on target groups.

The amine modified silica gel base material formed by grafting the primary, secondary and tertiary amine functional groups on the surface of the silica gel base through a synthetic method is also commonly used for adsorbing and purifying and removing partial low-valence, divalent and high-valence metal ion impurities in high-purity chemicals. According to different modifier functional groups, the amino modified silica gel material has different functions and is widely applied to biomedical, bactericide, metal ion treatment and other aspects.

Similarly, the silica gel is used as a matrix carrier, the organic matter containing the mercapto functional group is used as a modifier, and the prepared mercapto modified silica gel material also has excellent chemical stability and mechanical stability, is widely applied to biomedicine, bactericides, metal ion treatment and other aspects, and is especially used for purifying partial high-purity chemicals with high requirements on metal ion impurities, and is used for removing low-valence metal ions and heavy metal ions.

The modified silica gel base material is one of the important functional materials which are emerging in recent years, and is an important new material which is obtained by modification and synthesis on the basis of a silica gel particle matrix, has the characteristics of high specific surface area and high adsorption capacity, modification grafting of specific functional groups, adsorption purification of specific impurities, convenient separation and recovery and the like, and has many industrial applications in the aspects of solid acid catalysis, metal ion impurity adsorption purification and the like. However, most of researches on silica gel materials, modified silica gel materials and the like are focused on aqueous phase systems and adsorption of lead, mercury, cadmium, radioactive metal ions and heavy metal ions, and the modified silica gel new materials are rarely applied to the field of preparation of semiconductor electronic organic chemical materials, particularly application of key components such as semiconductor upstream resin materials with extremely high purification requirements.

4-Dimethylaminopyridine is a novel high-efficiency alkaline catalyst widely used for chemical synthesis in recent years, and the resonance of dimethylamino groups with electron donating structures and a parent ring (pyridine ring) can strongly activate nitrogen atoms on the ring to carry out nucleophilic substitution, and remarkably catalyze acylation (phosphorylation, sulfonylation and carboacylation) reactions of alcohols and amines with high steric hindrance and low reactivity, and the activity of the catalyst is about 104-6 times of that of pyridine. The catalyst has high catalytic capability in various reactions such as acylation, alkylation, etherification, esterification, transesterification and the like in organic synthesis, pharmaceutical synthesis, pesticides, medicines, dyes, fragrances, polymer chemistry and analytical chemistry.

After PHS resin for 248nm photoresist is organically synthesized, the conventional purification process for removing small molecular catalyst N, N-lutidine is complicated, the common purification method comprises the steps of using solid acid ion resin for slow adsorption neutralization, and the solid acid ion resin is required to be subjected to complicated pretreatment to remove small molecular acid substances capable of being dissolved out, so that other acid impurities are not introduced. Or the water washing extraction mode, not only introduces very high moisture, but also needs the procedures of drying the solution to remove the moisture and the like. These conventional approaches all result in significant loss of effectiveness of the resin.

Therefore, the catalyst of the resin synthesis process for PHS-type photoresists, namely, small organic molecule 4-N, N-dimethylaminopyridine, cannot survive after the reaction is completed. Because the chemically amplified resist has strict requirements on the pH of the resin product used, the alkaline and acidic substances need to have a residual value of < 1ppm, otherwise the working principle of the photoacid generator is seriously affected.

Therefore, it is necessary to separate and purify the small molecular catalyst 4-N, N-dimethylaminopyridine added during the reaction from the reaction liquid system after the completion of the catalytic synthesis reaction of the resin, and at the same time, other trace acidic or basic substances cannot be introduced to influence the photoacid generator to function.

Therefore, it is very necessary to develop a solid-based alkaline catalyst, which can overcome the defect that small molecular alkaline catalysts, such as small molecular 4-dimethylaminopyridine, are difficult to be purified and removed after catalytic synthesis as a catalyst, and can be a new material with purification function similar to other solid metal ion adsorbents.

In the process of using and researching the using function of the modified silica gel base material, the double functional groups of mercapto and 4-methylaminopyridine are grafted on the surface of the silica gel, and unreacted excessive small organic molecules adsorbed in the modified silica gel are very easy to obtain the solid double functional group modified silica gel without small molecule impurities in the material after simple washing treatment. Can replace small molecular alkaline catalyst 4-N, N-dimethyl pyridine. Can be used for replacing catalytic synthesis reaction to prepare t-BOC-PHS resin for chemical amplification type photoresist.

Meanwhile, the mercapto group and the 4-methylaminopyridine grafted on the surface of the modified silica gel matrix have the capability of partially purifying and adsorbing metal ion impurities due to the mercapto group and the weak alkaline amino functional groups, and the metal ion impurities in a reaction liquid system can be removed to be less than 5ppb in the reaction process.

Disclosure of Invention

The invention aims at providing a silica gel based material modified by a bifunctional group containing sulfhydryl and 4-methylaminopyridine, and applying the silica gel based material to the aspects of catalytic synthesis of a resin for chemical amplification type photoresist, purification of acid-base residual impurities and metal ion impurities. The catalyst has the advantages that the catalytic synthesis effect of substituting small molecule 4-N, N-dimethylaminopyridine is achieved, after the reaction is finished, only solid-liquid filtration separation is needed, the removal of the solid catalyst can be finished, and meanwhile, the catalyst has the effect of purifying and removing acid-base residual impurities and metal ion impurities in the solution, so that the problems of the catalytic synthesis of the t-BOC-PHS resin solution, the removal of alkaline small molecule catalyst, other acid-base residual impurities and the removal of metal ions are solved, and the material can be repeatedly used for catalyzing the reaction and purifying and removing the acid-base residual impurities and the metal ion impurities after simple reprocessing.

The invention provides a modified silica gel base material containing mercapto and 4-methylaminopyridine difunctional groups and a preparation method thereof. The mercapto group-containing and 4-methylaminopyridine difunctional groups are commonly grafted on the surface of silica gel to form the novel difunctional group-containing modified silica gel base material and the application thereof in the processes of catalyzing synthesis and purification of acid-base residual substances and removal of metal ion impurities of a class of chemically amplified photoresist resin.

The novel difunctional modified silica gel material related by the invention is not found to be used in the field of semiconductor electronic chemicals, and is not a modified silica gel base material which can be used as a synthesis catalyst and has the functions of removing acid-base residual impurities and purifying and removing metal ion impurities.

In order to achieve the aim of the invention, the invention provides a novel thiol-and 4-methylaminopyridine difunctional group-containing modified silica gel-based material, the chemical structure of which comprises one or more of the following structures:

Wherein,

The silicon atoms of the 4-methylaminopyridine and the trisiloxane group can be connected through one of methylene, ethyl and propyl;

The silica gel based material containing mercapto group and 4-methylaminopyridine difunctional group and represented by chemical formulas (I), (II) and (III) has the general physical properties necessary for general modified silica gel, and has the characteristics of high mechanical strength, light and heat stability similar to that of silica gel materials.

The silica gel based material containing mercapto and 4-methylaminopyridine difunctional group modification represented by the structural formulas (I), (II) and (III) can be used as a solid catalyst containing aminopyridine groups for catalytic esterification and catalytic acylation to synthesize small molecular compounds or high molecular compounds with ester groups such as-COO-, -OOC-, -CON-, and acyl groups;

The invention also provides a preparation method of the mercapto-and 4-methylaminopyridine difunctional group-containing modified silica gel-based material, which comprises the following chemical preparation steps:

(1) Adding 3-mercaptopropyl trimethoxy silane, silica gel, toluene and triethylamine into a reaction bottle, heating and refluxing under the protection of nitrogen, performing post-treatment, and drying to obtain mercapto-modified silica gel;

(2) A solid silane coupling agent is formed by 4-methylaminopyridine and 3-chloroalkyltrimethoxysilane; then adding sulfhydryl modified silica gel into toluene, heating and refluxing for reaction, post-treating, and drying to obtain the sulfhydryl and 4-methylaminopyridine difunctional group-containing modified silica gel material;

In the step (1), the mass ratio of the 3-mercaptopropyl trimethoxy silane to the silica gel to the toluene to the triethylamine is 10:20:60:1.

In step (1), the temperature of the reaction is 105-115 ℃.

In the step (1), the reaction time is 12-36 hours; preferably 24 hours.

In the step (2), the temperature of the reflux reaction is 105-115 ℃.

In the step (2), the reflux reaction time is 12-36 hours; preferably 24 hours.

In the step (2), the mass ratio of the silane coupling agent to the mercapto-modified silica gel is 1:1 to 1:4, a step of; preferably 1:2.

The invention also provides application of the mercapto-and 4-methylaminopyridine difunctional group-containing modified silica gel-based material in catalytic acylation reaction and catalytic esterification reaction.

The silica gel based material modified by the mercapto-and 4-methylaminopyridine difunctional groups has the chemical structure of the mercapto-and 4-methylaminopyridine difunctional groups, so that the silica gel based material has the chemical property of the mercapto-and amino pyridine difunctional groups and the alkaline catalytic property of the amino pyridine. Therefore, the silica gel based material modified by the difunctional groups containing the mercapto group and the 4-methylaminopyridine has one of the performances that the silica gel based material is used as a solid alkaline catalyst to replace small molecular 4-N, N-dimethylaminopyridine and is used as a catalyst of the solid based material to catalyze and synthesize small molecular compounds or high molecular compounds with acyl groups and ester groups.

The said compound has-COO-, -OOC-, and-CON-isopolyl in the small molecule or high molecular compound of acyl group, particularly preferred are the catalytic syntheses of compounds of the following structure:

the invention relates to a mercapto-and 4-methylaminopyridine difunctional group-containing modified silica gel-based material, which comprises the following steps of:

The modified silica gel containing mercapto and 4-methylaminopyridine difunctional groups is used as an alkaline catalyst and is added for catalyzing PHS and di-tert-butyl dicarbonate to react and synthesize t-BOC-PHS.

The chemical materials which are catalyzed and synthesized comprise ester bond or amide polymer substances or micromolecule substances, including m-cresol-formaldehyde resin, polyhydroxystyrene and copolymers thereof, polyacrylic acid derivatives; the chemical materials to be catalyzed and synthesized comprise resin materials for photoresist;

In the application, the solvent is an organic ether reagent, and the organic ether or ester reagent comprises ethyl lactate, propylene glycol methyl ether acetate, ethyl acetate, methyl acetate, acetone, toluene, methanol, ethanol and 4-heptanone.

The invention also provides application of the mercapto-and 4-methylaminopyridine difunctional group-containing modified silica gel-based material in purifying and removing impurities in a product solution system.

The impurities comprise metal ion impurities, acidic impurities and alkaline impurities in the solution.

The acidic impurities include inorganic acids and organic acids; the inorganic acid comprises hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid and oxalic acid; the organic acid comprises p-toluenesulfonic acid, camphorsulfonic acid, acetic acid and formic acid;

the alkaline impurities comprise organic amine alkaline substances;

The metal ion impurities include metal ion impurities containing metals and polyvalent metal ions of groups 3 to 12 from the 4 th to the 7 th periods.

The silica gel based material modified by the difunctional groups containing the mercapto group and the 4-methylaminopyridine has the advantages that the material itself has the mercapto group and the amino group capable of purifying and removing metal ions, and the metal ion impurities in the solution system after the reaction is finished can be effectively removed. Therefore, the modified silica gel base material is used as a solid base material with alkaline aminopyridine groups, and small molecular alkaline substances which are difficult to purify and remove are not introduced into a reaction system. Meanwhile, acidic substances in the solution system are naturally neutralized by the solid basic groups and then filtered and removed. The synthesis and purification of photoresist resin electronic chemicals with high requirements on reaction and purification are obviously improved.

The invention also provides a catalytic synthesis method of the resin for the semiconductor photoresist, wherein in the catalytic synthesis reaction, the modified silica gel base material containing the mercapto group and the 4-methylaminopyridine difunctional group is used as a catalyst.

The invention also provides a method for removing impurities after the completion of the resin catalytic synthesis reaction, wherein the modified silica gel base material containing mercapto and 4-methylaminopyridine difunctional groups is added; the impurities include metal ion impurities, acidic impurities and alkaline impurities.

The invention also provides a use method of the modified silica gel base material containing mercapto and 4-methylaminopyridine difunctional groups, which comprises the following steps:

Taking the modified silica gel base material containing mercapto and 4-methylaminopyridine difunctional groups as a solid catalyst to perform catalytic synthesis acylation reaction or esterification reaction; after the reaction is finished, the solid and the liquid are simply separated through a filtering and separating device, and the solution of the required product is obtained.

The difunctional group modified silica gel base material containing mercapto groups and 4-methylaminopyridine of the invention has the following purification performance on a solution system:

after the reaction solution system is finished, the solution system is simply filtered and separated, and the liquid product and the solid modified silica gel material are separated. No other complicated purification steps are required.

The method provided by the invention has the advantages that the content of main metal ion impurities in the product solution is greatly reduced to below 5ppb, and micromolecular acid-base residual impurities in the liquid product can be removed to below 1 ppm.

The invention has the beneficial effects that: the novel modified silica gel base material containing mercapto and 4-methylaminopyridine difunctional groups, which is innovatively provided by the invention, can be prepared according to a conventional preparation method. The modified silica gel-based material containing mercapto and 4-methylaminopyridine difunctional groups, which is obtained by the invention, has excellent alkaline catalytic acylation performance and catalytic esterification performance. The invention has the excellent characteristics of low catalyst usage amount, easy filtration and separation and low metal ion impurity content when the modified silica gel base material containing mercapto and 4-methylaminopyridine difunctional groups is used as a catalyst for catalytic acylation and catalytic esterification. The method has better application in the aspects of preparing 248nm photoresist by resin catalytic synthesis, removing acid-base residual impurities and removing metal ion impurities.

Detailed Description

The invention is further illustrated below in connection with specific embodiments, which are, however, examples of the invention, which are not limited to the following examples.

It will be apparent to those skilled in the art that other publicly available synthetic methods can be used to prepare the modified silica gel-based materials containing mercapto and 4-methylaminopyridine difunctional groups referred to in the present invention without departing from the spirit or scope of the present invention. These synthetic techniques are conventional and the resulting compounds meet the organic fine electronic chemical standards.

In the following examples, which relate specifically to catalytic and purification properties of modified silica gel based materials containing mercapto and 4-methylaminopyridine difunctional groups, the scope of the claims is not limited to the examples.

The following shows the results of the application tests of the preparation of the modified silica gel-based materials each containing mercapto and 4-methylaminopyridine difunctional groups, the catalytic reaction thereof and the purification of impurities.

Example 1: thiol-and 4-methylaminopyridine difunctional group-containing modified silica gel base material

(1) Preparing an intermediate sulfhydryl modified silica gel material:

80g of silica gel, 240g of toluene, 4g of triethylamine and 40g of 3-mercaptopropyl trimethoxysilane are introduced into a 1L three-port reaction flask. Stirring is started, and the stirring speed is 200 revolutions per minute; the system is replaced by nitrogen, so that the nitrogen atmosphere of the system is ensured; and (3) slightly opening a steam heating valve, and controlling the feed liquid to keep backflow. The reaction was stirred at 110℃for 24 hours. Cooling to room temperature. Removing the solvent and unreacted raw materials by reduced pressure suction filtration until the raw materials are dried;

then adding 150ml of ethyl acetate into the 1L three-mouth bottle, adding the filtered solid, stirring for 30min, and filtering (toluene after filtering is concentrated and stored for recovery); repeating the steps twice;

Then adding 150ml of ethanol into the 1L three-mouth bottle, adding the filtered solid, stirring for 30min, and filtering; repeatedly taking ethanol liquid for detection twice until the maximum impurity is less than 0.02%;

Then adding 150ml pure water into the 1L three-mouth bottle, adding the filtered solid, stirring for 30min, filtering, and repeating twice;

Then adding 150ml of ethanol into the 1L three-mouth bottle, adding the filtered solid, stirring for 30min, and filtering;

taking out the silica gel, filtering and drying the silica gel, and drying the silica gel at 80 ℃ for 12 hours to obtain 100g of intermediate sulfhydryl modified silica gel. And (5) drying and preserving.

(2) Preparation of thiol-containing, 4-methylaminopyridine difunctional group modified silica gel:

100g of the intermediate mercapto-modified silica gel prepared in the above step, 300g of toluene, 5g of triethylamine, and 50g of 3-4-methylaminopyridine trimethoxysilane were added into a 1L three-port reaction flask. Stirring is started, and the stirring speed is 200 revolutions per minute; the system is replaced by nitrogen, so that the nitrogen atmosphere of the system is ensured; and (3) slightly opening a steam heating valve, and controlling the feed liquid to keep backflow. The reaction was stirred at 110℃for 48 hours. Cooling to room temperature. Removing the solvent and unreacted raw materials by reduced pressure suction filtration until the raw materials are dried;

Then adding 200ml of ethyl acetate into the 1L three-mouth bottle, adding the filtered solid, stirring for 30min, and filtering (the filtered ethyl acetate is stored in a concentrated way to be recovered); repeating the steps twice;

adding 200ml of ethanol into the 1L three-mouth bottle, adding the filtered solid, stirring for 30min, and filtering (the filtered ethanol is stored in a concentrated way and is recovered); repeating the steps twice; taking ethanol liquid for detection until the maximum impurity is less than 0.02%; the 50L kettle was charged with 200ml pure water, the filtered solid was added and stirred for 30min, filtered, and repeated twice.

Adding 200ml ethanol into the 1L three-mouth bottle, adding the filtered solid, stirring for 30min, and filtering;

Taking out the silica gel, and putting the silica gel into an oven to be dried for 12 hours at 80 ℃ to obtain 130g of modified silica gel base material containing mercapto and 4-methylaminopyridine difunctional groups. Drying and sealing for preservation.

Example 2 catalytic synthesis example;

Taking 0.1g of the dried silica gel base material containing mercapto group and 4-methylaminopyridine difunctional groups, which is obtained in the embodiment 1, adding the silica gel base material into a 250 ml three-port reaction bottle, adding 100ml of a reaction solvent PMA, adding 25g of solid PHS (polyvinyl phenol) powder, 12g of di-tert-butyl dicarbonate, and reacting for 12 hours at room temperature under the protection of nitrogen, and ending the reaction to obtain a reaction liquid 1. Then sampling and detecting the content of t-BOC-PHS, the residual quantity of di-tert-butyl dicarbonate and the molecular weight of the resin.

After the reaction is finished, filtering and separating a solid-liquid mixture of a product after the reaction in a dust-free laboratory under the protection of nitrogen by using a PTFE microfiltration membrane with a 1um aperture and a filter. Sampling and detecting metal ion impurities and amine small molecule impurities, and the results are shown in Table 1.

Example 3:

taking 0.015g of 4-N, N-dimethylaminopyridine, adding the mixture into a 250 ml three-port reaction bottle, adding 100ml of a reaction solvent PMA, adding 25g of solid PHS (polyvinyl phenol) powder, 12g of di-tert-butyl dicarbonate, protecting by nitrogen, and reacting at room temperature for 12 hours to finish the reaction to obtain a reaction liquid 2. And (3) sampling and detecting the content of t-BOC-PHS, the residual quantity of di-tert-butyl dicarbonate and the molecular weight of the resin.

After the reaction is finished, sampling and detecting metal ion impurities and amine micromolecular impurities in a dust-free laboratory under the protection of nitrogen. Table 1 below shows the product, organic impurities, raw material residue, and molecular weight data of the comparative reaction solution (reaction solution 2):

TABLE 1

Example 4

The metal ion impurity data table of the thiol-containing, 4-methylaminopyridine difunctional group-containing modified silica gel based material purified resin product prepared by example 1 of the present invention is shown in table 3 below:

Comparison experiment: the product solution after filtration by the method of the invention is compared with metal ion impurities of other purification methods:

after the catalyst is used for synthesizing the t-BOC-PHS reaction liquid by catalytic synthesis of the thiol-containing and 4-methylaminopyridine difunctional group modified silica gel base material, the reaction liquid is subjected to different purification methods with the reaction liquid obtained after the catalytic synthesis of the conventional 4-N, N-dimethylaminopyridine to obtain a product solution, and the product solution is subjected to comparison of alkaline substance residues and metal ion impurity purification data comparison:

The results of the small molecule amine residue (GC test) and the main metal ion impurity (ICP-MS test) of the original reaction solution after catalysis and the purified resin solution for the two different catalysts are shown in table 2 below:

TABLE 2

Example 5 other modes of purification of metal ion impurities data comparison

Comparison experiment: the product solution after filtration by the method of the invention is compared with metal ion impurities of other purification methods:

after the catalyst is used for synthesizing the t-BOC-PHS reaction liquid by catalytic synthesis of the thiol-containing and 4-methylaminopyridine difunctional group modified silica gel base material, the reaction liquid is subjected to different purification methods with the reaction liquid obtained after the catalytic synthesis of the conventional 4-N, N-dimethylaminopyridine to obtain a product solution, and the product solution is subjected to comparison of alkaline substance residues and metal ion impurity purification data comparison:

the results of the small molecule amine residue (GC test) and the main metal ion impurity (ICP-MS test) of the original reaction solution after catalysis and the purified resin solution for the two different catalysts are shown in table 3 below:

TABLE 3 Table 3

The above embodiments are merely specific examples that are generally representative.

While the invention has been described above with respect to a general description and specific embodiments, they are representative examples of the invention and many modifications and improvements thereto will become apparent to those skilled in the art based on the present invention. Accordingly, the invention is not limited by the foregoing description, and modifications or improvements may be made without departing from the scope of the invention.

Claims (10)

1. A modified silica gel-based material containing mercapto and 4-methylaminopyridine difunctional groups is characterized in that: the structure of the compound comprises one or more of the following formulas (I), (II) and (III):

2. The method for preparing a modified silica gel-based material containing mercapto groups and 4-methylaminopyridine difunctional groups according to claim 1, wherein the modified silica gel-based material is prepared by the following synthetic method: a synthesis method of grafting mercapto and then grafting 4-methylaminopyridine functional groups, or a synthesis method of simultaneously grafting mercapto and 4-methylaminopyridine two different chemical functional groups onto silica gel groups.

3. The preparation method according to claim 2, characterized in that the method comprises the following specific steps:

(1) Adding 3-mercaptopropyl trimethoxy silane, silica gel, toluene and triethylamine into a reaction bottle, heating and refluxing under the protection of nitrogen, performing post-treatment, and drying to obtain mercapto-modified silica gel;

(2) A solid silane coupling agent is formed by 4-methylaminopyridine and 3-chloroalkyltrimethoxysilane; then adding sulfhydryl modified silica gel into toluene, heating and refluxing for reaction, post-treating, and drying to obtain the sulfhydryl and 4-methylaminopyridine difunctional group-containing modified silica gel material.

4. The preparation method according to claim 3, wherein in the step (1), the mass ratio of the 3-mercaptopropyl trimethoxysilane, the silica gel, the toluene and the triethylamine is 10:20:60:1, a step of; the temperature of the reaction is 105-115 ℃; the reaction time is 12-36 hours;

In the step (2), the temperature of the reflux reaction is 105-115 ℃; the reflux reaction time is 12-36 hours; the mass ratio of the silane coupling agent to the mercapto-modified silica gel is 1:1-1:4.

5. Use of a modified silica gel based material containing mercapto and 4-methylaminopyridine difunctional groups according to claim 1 as basic catalyst for resin catalyzed synthesis reactions; or, after the resin catalytic synthesis reaction is completed, removing metal ion impurities, acidic impurities and alkaline impurities in the solution.

6. The use according to claim 5, wherein,

In the application, the chemical materials which are catalyzed and synthesized comprise high molecular substances or small molecular substances containing ester bonds or amides, including m-cresol-formaldehyde resin, polyhydroxystyrene and copolymers thereof, polyacrylic acid derivatives; the chemical materials to be catalyzed and synthesized comprise resin materials for photoresist;

In the application, the solvent is an organic ether reagent, and the organic ether or ester reagent comprises ethyl lactate, propylene glycol methyl ether acetate, ethyl acetate, methyl acetate, acetone, toluene, methanol, ethanol and 4-heptanone.

7. The use according to claim 5, wherein, in said use,

The acidic impurities include inorganic acids and organic acids; the inorganic acid comprises hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid and oxalic acid; the organic acid comprises p-toluenesulfonic acid, camphorsulfonic acid, acetic acid and formic acid;

the alkaline impurities comprise organic amine alkaline substances;

The metal ion impurities include metal ion impurities containing metals and polyvalent metal ions of groups 3 to 12 from the 4 th to the 7 th periods.

8. A method for catalytic synthesis of a resin for semiconductor photoresist, characterized in that the modified silica gel-based material containing mercapto and 4-methylaminopyridine bifunctional group as defined in claim 1 is used as a catalyst in the catalytic synthesis reaction.

9. A method for removing impurities after completion of the resin catalytic synthesis reaction, characterized in that the modified silica gel-based material containing mercapto group and 4-methylaminopyridine bifunctional group as described in claim 1 is added thereto; the impurities include metal ion impurities, acidic impurities and alkaline impurities.

10. A method of using the modified silica gel based material having mercapto-and 4-methylaminopyridine difunctional groups according to claim 1, said method comprising the steps of:

Taking the modified silica gel base material containing mercapto and 4-methylaminopyridine difunctional groups as a solid catalyst to perform catalytic synthesis acylation reaction or esterification reaction; after the reaction is finished, the solid and the liquid are simply separated through a filtering and separating device, and the solution of the required product is obtained.