CN111138405A - Sulfonium sulfonate photo-acid generator synthesized from patchouli alcohol and synthesis method thereof - Google Patents
Sulfonium sulfonate photo-acid generator synthesized from patchouli alcohol and synthesis method thereof Download PDFInfo
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- CN111138405A CN111138405A CN201911384565.3A CN201911384565A CN111138405A CN 111138405 A CN111138405 A CN 111138405A CN 201911384565 A CN201911384565 A CN 201911384565A CN 111138405 A CN111138405 A CN 111138405A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
- C07D333/10—Thiophene
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
- C07C309/12—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing esterified hydroxy groups bound to the carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
Abstract
The invention discloses a sulfonium sulfonate photo-acid generator synthesized by patchouli alcohol and a synthesis method thereof, belonging to the field of chemical synthesis and photoetching materials. The general structural formula of the photoacid generator is as follows:
in the formula, R1Is composed of
And
one of (1); r2Is one of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, ester-containing alkyl and fluoroalkyl. The synthetic method of the photoacid generator comprises the following steps: reacting patchouli alcohol with a sulfonate compound to obtain an intermediate; and (2) reacting the intermediate with (cyclohexyl-1, 5-dialkenyloxy) -trimethyl-silane, tetramethylene sulfoxide and trifluoroacetic anhydride to obtain the sulfonium sulfonate photo-acid generator. The patchouli alcohol used as the raw material has higher molecular weight, and the formed photoacid generator also has higher molecular weight, so that the diffusion of the photoacid generator can be reduced, the improvement of edge roughness is facilitated, the line width roughness is reduced, and the resolution is improved.
Description
Technical Field
The invention relates to the field of chemical synthesis and photoetching materials, in particular to a sulfonium sulfonate photo-acid generator synthesized by patchouli alcohol and a synthesis method thereof.
Background
The photolithography technique is a fine processing technique for transferring a pattern designed on a mask plate to a pattern on a substrate by using the chemical sensitivity of a photolithography material (particularly a photoresist) under the action of visible light, ultraviolet rays, electron beams and the like through the processes of exposure, development, etching and the like.
The development of the lithography technology is not independent of the development of the lithography material, and the development of the lithography material determines the development and application of the lithography technology to a certain extent. The photolithography material (specifically referred to as photoresist), also called photoresist, is the most critical functional chemical material involved in photolithography technology, and its main components are resin, Photo Acid Generator (PAG), and corresponding additives and solvents. The photoacid generator is a photosensitive compound, which decomposes under light irradiation to generate an acid, which can decompose or crosslink the acid-sensitive resin, thereby increasing the dissolution contrast between the irradiated part and the non-irradiated part in a developer, and can be used in the technical field of pattern microfabrication.
With the development of large-scale and ultra-large-scale integrated circuits in recent years, the research, development and application of photoresist are greatly promoted. As the feature size of integrated circuits decreases, the effect of edge roughness becomes more pronounced and the types of photoacid generators are developed. However, the conventional photoacid generator still has a problem of diffusion of acid, and thus edge roughness cannot be reduced.
Disclosure of Invention
An object of the embodiments of the present invention is to provide a sulfonium sulfonate photoacid generator synthesized from patchouli alcohol, so as to solve the problems in the background art.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
a sulfonic sulfonium salt photo-acid generator synthesized by patchouli alcohol has a structural general formula I:
in the formula, R1Is composed of
One of (1); r2Is one of alkyl, cycloalkyl, ester group-containing alkyl and fluorine-containing alkyl.
As a preferred embodiment of the present invention, the structural formula of the sulfonium sulfonate salt photoacid generator is one of formula II, formula III, formula IV and formula V:
another object of the embodiments of the present invention is to provide a method for synthesizing the above sulfonium sulfonate photoacid generator, which comprises the following steps:
reacting patchouli alcohol with a sulfonate compound to obtain an intermediate;
and (2) reacting the intermediate with (cyclohexyl-1, 5-dialkenyloxy) -trimethyl-silane, tetramethylene sulfoxide and trifluoroacetic anhydride to obtain the sulfonium sulfonate photo-acid generator.
As another preferable mode of the embodiment of the present invention, the sulfonate compound is a carboxyl group-containing sulfonate; the method comprises the following steps of reacting patchouli alcohol with a sulfonate compound to obtain an intermediate, and specifically comprises the following steps:
carrying out esterification reaction on patchouli alcohol and sulfonate containing carboxyl to obtain an intermediate; the intermediate is sulfonate containing patchouli alcohol ester group.
Wherein the techniqueR in formula of sulfonium sulfonate photo-acid generator obtained by the technical scheme1Is composed of
As another preferable mode of the embodiment of the present invention, the sulfonate compound is a hydroxyl group-containing sulfonate; the method comprises the following steps of reacting patchouli alcohol with a sulfonate compound to obtain an intermediate, and specifically comprises the following steps:
reacting patchouli alcohol with hydroxyl-containing sulfonate to obtain an intermediate; the intermediate is sulfonate containing patchouli alcohol carbonate group.
Wherein R in the formula of the sulfonic sulfonium salt type photoacid generator obtained by the technical scheme1Is composed of
As another preferable mode of the embodiment of the present invention, the sulfonate compound is a hydroxyl group-containing sulfonate; the method comprises the following steps of reacting patchouli alcohol with a sulfonate compound to obtain an intermediate, and specifically comprises the following steps:
reacting patchouli alcohol with ester-group-containing halide to obtain an ester-group-containing ether compound;
hydrolyzing the ester group of the ether compound containing the ester group under an alkaline condition, and adjusting the ester group to be acidic to obtain an ether compound containing a carboxyl group;
carrying out esterification reaction on the ether compound containing carboxyl and sulfonate containing hydroxyl to obtain an intermediate; the intermediate is sulfonate containing ester group.
Wherein R in the formula of the sulfonic sulfonium salt type photoacid generator obtained by the technical scheme1Is composed of
In another preferable embodiment of the present invention, the sulfonate compound is one of a sodium sulfonate compound, a potassium sulfonate compound, and a lithium sulfonate compound.
As another preferable mode of the embodiment of the present invention, p-toluenesulfonic acid is used as a catalyst in the esterification reaction.
As another preferable scheme of the embodiment of the present invention, the step of reacting patchouli alcohol with hydroxyl group-containing sulfonate to obtain an intermediate specifically includes:
placing patchouli alcohol and sulfonate containing hydroxyl in a system containing pyridine and bis (trichloromethyl) carbonate for reaction to obtain an intermediate.
As another preferable mode of the embodiment of the present invention, the ester group-containing halide is an ester group-containing bromide.
Another object of the embodiments of the present invention is to provide an application of the above sulfonic acid sulfonium salt photoacid generator synthesized from patchouli alcohol in a lithography material.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
(1) the synthesis raw material patchouli alcohol adopted by the sulfonium sulfonate photoacid generator provided by the embodiment of the invention has higher molecular weight, and the formed photoacid generator also has higher molecular weight, so that the exposure and postbaking processes of photoetching and the diffusion of acid generated in an exposure area are reduced, the edge roughness of a photoetching pattern is favorably improved, the line width roughness is reduced, and the pattern resolution is improved.
(2) The sulfonium sulfonate photoacid generator provided by the embodiment of the invention contains an ester group, so that the lipid solubility of the photoacid generator can be increased, the photoacid generator is more easily dissolved in a solvent, the polarity of the photoacid generator and resin is closer, the resin and the photoacid generator are more uniformly mixed in the solvent, and the formation of more uniform photoresist is facilitated.
(3) The sulfonium sulfonate photo-acid generator provided by the embodiment of the invention contains aliphatic rings, and has excellent etching resistance.
(4) The sulfonium sulfonate photoacid generator provided by the embodiment of the invention has a simple synthetic route and is convenient to prepare and generate.
(5) The sulfonium sulfonate photo-acid generator provided by the embodiment of the invention does not contain benzene rings, has better transparency at 193nm, and has less influence on the transparency of 193nm photoresist when the 193nm photoresist is formed by doping, thereby being beneficial to better exposure of the photoresist.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This example provides a sulfonic acid sulfonium salt photoacid generator synthesized from patchouli alcohol, the reaction route of the synthesis method of the photoacid generator is as follows:
the method specifically comprises the following steps:
s1, dissolving sodium hydroxide (14g, 350mmol) in water (60g) to prepare a 30% sodium hydroxide solution; adding methyl fluorosulfonyl difluoroacetate (20g, 104mmol) into ice water (200g) to obtain a reaction solution, slowly adding a prepared 30% sodium hydroxide solution into the reaction solution under stirring, stirring the reaction solution in an ice bath (the temperature is controlled to be lower than 10 ℃) for 2.5 hours after the addition is finished, then continuing stirring at room temperature for 1 hour, starting heating until the temperature rises to 95 ℃ within 30 minutes, stirring at 95 ℃ for 3 hours, stopping heating, cooling to room temperature, neutralizing with hydrochloric acid, filtering the reaction solution, collecting a filtrate, adding acetone (1200g) into the filtrate, separating out a white solid, filtering, washing a filter cake with acetone (120g), and drying to obtain a compound 1-2(21.6g, 98mmol, 94% yield).
S2, compound 1-2(21.6g, 98mmol) was added to acetonitrile (300g), p-toluenesulfonic acid monohydrate (28g, 147mmol) was added thereto, and the mixture was stirred at room temperature for 30 minutes to obtain a reaction solution, and then the reaction solution was heated to 80 degrees celsius, and after stirring at 80 degrees celsius for 3 hours, the reaction solution was cooled to room temperature, filtered, and the filter cake was dried to obtain compound 1-3(14g, 71mmol, yield 72%) as a white solid.
S3, adding compound 1-3(14g, 71mmol), patchouli alcohol (16g, 72mmol) and p-toluenesulfonic acid monohydrate (2g, 10.5mmol) to 400g of toluene to obtain a reaction solution, refluxing the reaction solution for 18 hours, and cooling to room temperature to obtain a mixture; then, the mixture was filtered to obtain a solid, the solid was washed three times with acetonitrile, an acetonitrile solution was collected, and the collected acetonitrile solution was concentrated and added to methyl t-butyl ether (200g) to carry out beating to obtain a mixed solution, the above mixed solution was filtered, and the cake was collected and dried to obtain intermediates 1 to 4(26g, 65mmol, yield 91.4%) as a solid.
S4, (cyclohexa-1, 5-dienyloxy) -trimethyl-silane (11g, 65mmol) and tetramethylene sulfoxide (7g, 67mmol) were dissolved in chloroform (600g) under nitrogen flow and cooled to-30 ℃, then trifluoroacetic anhydride (21g, 100mmol) was slowly added over 30 minutes, after stirring for reaction for 30 minutes, a saturated aqueous solution of the above-mentioned intermediate 1-4(26g, 65mmol) was further added with stirring and stirring for reaction for 1 hour, after the reaction was completed, water and chloroform were separated, the aqueous phase was extracted with chloroform, the chloroform phase was concentrated under vacuum to give a crude product, which was washed with diisopropyl ether to give sulfonic sulfonium salt photoacid generator 1-5(30g, 53mmol, 82% yield).
Example 2
This example provides a sulfonic acid sulfonium salt photoacid generator synthesized from patchouli alcohol, the reaction route of the synthesis method of the photoacid generator is as follows:
the method specifically comprises the following steps:
s1, under the protection of nitrogen at 0 ℃, adding pyridine (18g, 228mmol) and bis (trichloromethyl) carbonate (9g, 30mmol) into dichloromethane (400g), and slowly adding patchouli alcohol 2-1(20g, 90mmol) under stirring to obtain a reaction solution; next, the reaction solution was left at room temperature and stirred for 3 hours, then 1, 1-difluoro-2-hydroxy-ethanesulfonic acid sodium salt (17g, 92mmol) was added to the reaction solution, stirred for 10 hours, the reaction solution was concentrated under vacuum to give a mixture, the mixture was filtered to give a solid, the solid was washed three times with acetonitrile, the acetonitrile solution was collected, the collected acetonitrile solution was concentrated and added to methyl tert-butyl ether for beating to give a mixed solution, the above mixed solution was filtered, and the oven-dried cake was collected to give intermediate 2-2(35g, 81mmol, yield 90%) as a solid.
S2, (cyclohexa-1, 5-dienyloxy) -trimethyl-silane (13.8g, 82mmol) and tetramethylene sulfoxide (9g, 86mmol) were dissolved in chloroform (700g) under nitrogen flow and cooled to-30 ℃, trifluoroacetic anhydride (26g, 124mmol) was slowly added over 30 minutes, after stirring for reaction for 30 minutes, a saturated aqueous solution of the above intermediate 2-2(35g, 81mmol) was further added with stirring and stirring for reaction for 1 hour, after the reaction was completed, water and chloroform were separated, the aqueous phase was extracted with chloroform, the chloroform phase was concentrated under vacuum to give a crude product, which was washed with methyl tert-butyl ether and dried to give a sulfonium sulfonate photoacid generator 2-3(39.5g, 67mmol, 82% yield).
Example 3
This example provides a sulfonic acid sulfonium salt photoacid generator synthesized from patchouli alcohol, the reaction route of the synthesis method of the photoacid generator is as follows:
the method specifically comprises the following steps:
s1, slowly adding sodium hydride (3.4g, 141mmol) to a mixture of patchouli alcohol 3-1(20g, 90mmol) and anhydrous tetrahydrofuran (300g) at 0 ℃ under nitrogen, and stirring for 20 minutes; ethyl bromoacetate (15.3g, 92mmol) was then added dropwise to the mixture, and the mixture was stirred for 20 minutes; then, the reaction was carried out by stirring at 25 ℃ for 6 hours, and after completion of the reaction, water was added thereto to quench at 0 ℃. Concentrating the quenched mixed solution by rotary evaporation, extracting with ethyl acetate (200g multiplied by 3) for three times, combining the extract, washing with saturated saline solution (300g), drying with anhydrous sodium sulfate, and concentrating by rotary evaporation to obtain a crude product; the crude product was purified by column chromatography to give compound 3-2(23g, 75mmol, yield 83%).
S2, adding the compound 3-2(23g, 75mmol) and sodium hydroxide (4.5g, 113mmol) into a mixed solution of water (40g) and methanol (160g), and stirring at 25 ℃ for 24h to obtain a reaction solution; then, concentrating the reaction solution, and adjusting the pH value of the reaction solution to 2 by using hydrochloric acid to obtain a mixed solution; then, the resulting mixture was extracted three times with ethyl acetate (200g × 3), the extracts were combined, washed with saturated brine (200g), dried over anhydrous sodium sulfate, and concentrated by rotary evaporation to obtain compound 3-3(19g, 68mmol, yield 90.8%) as a liquid.
S3, compound 3-3(19g, 68mmol), 1-difluoro-2-hydroxy-ethanesulfonic acid sodium salt (13g, 71mmol) and p-toluenesulfonic acid monohydrate (2g, 10.5mmol) were added to toluene (500g), and after heating to reflux for 18 hours, cooled to room temperature again, to give a mixture. Subsequently, the mixture was filtered to obtain a solid, which was washed three times with acetonitrile, and the acetonitrile solution was collected. The collected acetonitrile solution was concentrated and added to methyl t-butyl ether for pulping, the above mixture was filtered, and the dried cake was collected to obtain intermediate 3-4(24g, 54mmol, yield 79%) as a solid.
S4, (cyclohexyl-1, 5-dialkenyloxy) -trimethyl-silane (9.4g, 56mmol) and tetramethylene sulfoxide (5.8g, 56mmol) are dissolved in chloroform (500g) under the protection of nitrogen flow and cooled to-30 ℃, then trifluoroacetic anhydride (17g, 81mmol) is slowly added within 30 minutes, after stirring for reaction for 30 minutes, a saturated aqueous solution of the above intermediate 3-4(24g, 54mmol) is further added with stirring and stirring for reaction for 1 hour, after the reaction is finished, the temperature is returned to room temperature, water and chloroform are separated, the aqueous phase is extracted with chloroform, the chloroform phase is concentrated under vacuum to obtain a crude product, which is washed with methyl tert-butyl ether and dried to obtain 3-5(28g, 46mmol, 83% yield) of the sulfonic sulfonium salt photoacid generator.
Example 4
This example provides a sulfonic acid sulfonium salt photoacid generator synthesized from patchouli alcohol, the reaction route of the synthesis method of the photoacid generator is as follows:
the method specifically comprises the following steps:
s1, slowly adding sodium hydride (2.5g, 104mmol) to a mixture of patchouli alcohol 4-1(20g, 90mmol) and anhydrous tetrahydrofuran (400g) at 0 ℃ under nitrogen, and stirring for 20 minutes; then, ethyl 2-bromo-2-cyclopentylacetate (21.6g, 92mmol) was added dropwise to the above mixed solution, and stirred for 20 minutes; then, the reaction was carried out by stirring at 25 ℃ for 6 hours, and after completion of the reaction, water was added thereto to quench at 0 ℃. Concentrating the quenched mixture by rotary evaporation, extracting with dichloromethane (100g × 3) for three times, combining the extracts, washing with saturated saline (100g), drying with anhydrous sodium sulfate, and concentrating by rotary evaporation to obtain a crude product; the crude product was purified by column chromatography to give compound 4-2(30g, 80mmol, 89% yield).
S2, adding the compound 4-2(30g, 80mmol) and sodium hydroxide (5g, 125mmol) into a mixed solution of water (70g) and methanol (280g), and stirring at 25 ℃ for 24h to obtain a reaction solution; then, concentrating the reaction solution, and adjusting the pH value of the reaction solution to 2 by using hydrochloric acid to obtain a mixed solution; then, the resulting mixture was extracted three times with ethyl acetate (300g × 3), the extracts were combined, washed with saturated brine (200g), dried over anhydrous sodium sulfate, and concentrated by rotary evaporation to give compound 4-3(27g, 77.5mmol, yield 97.2%) as a liquid.
S3, compound 4-3(27g, 77.5mmol), 1-difluoro-2-hydroxy-ethanesulfonic acid sodium salt (15g, 81.5mmol) and p-toluenesulfonic acid monohydrate (2g, 10.5mmol) were added to toluene (600g), and after heating to reflux for 18 hours, cooled to room temperature again, to give a mixture. Subsequently, the mixture was filtered to obtain a solid, which was washed three times with acetonitrile, and the acetonitrile solution was collected. The collected acetonitrile solution was concentrated and added to methyl t-butyl ether for pulping, the above mixture was filtered, and the dried cake was collected to obtain intermediate 4-4(30g, 58mmol, yield 75.3%) as a solid.
S4, (cyclohexane-1, 5-dialkenyloxy) -trimethyl-silane (10g, 59mmol) and tetramethylene sulfoxide (6.5g, 62mmol) are dissolved in chloroform (550g) under the protection of nitrogen flow and cooled to-30 ℃, then trifluoroacetic anhydride (19g, 90mmol) is slowly added within 30 minutes, after stirring for reaction for 30 minutes, a saturated aqueous solution of the above intermediate 4-4(30g, 58mmol) is further added with stirring and stirring for reaction for 1 hour, after the reaction is finished, water and chloroform are separated, the aqueous phase is extracted with chloroform, the chloroform phase is concentrated under vacuum to obtain a crude product, which is washed with methyl tert-butyl ether and dried to obtain sulfonic sulfonium salt photoacid generator 4-5(31g, 46mmol, yield 73.6%).
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. The sulfonium sulfonate photoacid generator is synthesized from patchouli alcohol and is characterized in that the structural general formula of the sulfonium sulfonate photoacid generator is shown as formula I:
in the formula, R1Is composed of
One of (1); r2Is one of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, ester-containing alkyl and fluoroalkyl.
2. The sulfonium sulfonate photoacid generator synthesized from patchouli alcohol of claim 1, wherein the sulfonium sulfonate photoacid generator has a structural formula of one of formula II, formula III, formula IV and formula V:
3. a synthesis method of the sulfonic acid sulfonium salt photoacid generator synthesized from patchouli alcohol as claimed in any one of claims 1 to 2, comprising the steps of:
reacting patchouli alcohol with a sulfonate compound to obtain an intermediate;
and (2) reacting the intermediate with (cyclohexyl-1, 5-dialkenyloxy) -trimethyl-silane, tetramethylene sulfoxide and trifluoroacetic anhydride to obtain the sulfonium sulfonate photo-acid generator.
4. The method for synthesizing the sulfonium sulfonate photoacid generator synthesized from patchouli alcohol as claimed in claim 3, wherein the sulfonate compound is a carboxyl-containing sulfonate; the method comprises the following steps of reacting patchouli alcohol with a sulfonate compound to obtain an intermediate, and specifically comprises the following steps:
carrying out esterification reaction on patchouli alcohol and sulfonate containing carboxyl to obtain an intermediate; the intermediate is sulfonate containing patchouli alcohol ester group.
5. The method for synthesizing the sulfonium sulfonate photoacid generator synthesized from patchouli alcohol as claimed in claim 3, wherein the sulfonate compound is a hydroxyl group-containing sulfonate; the method comprises the following steps of reacting patchouli alcohol with a sulfonate compound to obtain an intermediate, and specifically comprises the following steps:
reacting patchouli alcohol with hydroxyl-containing sulfonate to obtain an intermediate; the intermediate is sulfonate containing patchouli alcohol carbonate group.
6. The method for synthesizing the sulfonium sulfonate photoacid generator synthesized from patchouli alcohol as claimed in claim 3, wherein the sulfonate compound is a hydroxyl group-containing sulfonate; the method comprises the following steps of reacting patchouli alcohol with a sulfonate compound to obtain an intermediate, and specifically comprises the following steps:
reacting patchouli alcohol with ester-group-containing halide to obtain an ester-group-containing ether compound;
hydrolyzing the ester group of the ether compound containing the ester group under an alkaline condition, and adjusting the ester group to be acidic to obtain an ether compound containing a carboxyl group;
carrying out esterification reaction on the ether compound containing carboxyl and sulfonate containing hydroxyl to obtain an intermediate; the intermediate is sulfonate containing ester group.
7. The method for synthesizing the sulfonium sulfonate photoacid generator synthesized from patchouli alcohol as claimed in any one of claims 4 to 6, wherein the sulfonate compound is one of sodium sulfonate compound, potassium sulfonate compound and lithium sulfonate compound.
8. The method for synthesizing the sulfonium sulfonate photoacid generator synthesized from patchouli alcohol as claimed in claim 4 or 6, wherein p-methyl benzene sulfonic acid is used as a catalyst in the esterification reaction.
9. The method for synthesizing the sulfonium sulfonate photoacid generator from patchouli alcohol as claimed in claim 5, wherein the step of reacting patchouli alcohol with hydroxyl group-containing sulfonate to obtain an intermediate specifically comprises:
placing patchouli alcohol and sulfonate containing hydroxyl in a system containing pyridine and bis (trichloromethyl) carbonate for reaction to obtain an intermediate.
10. Use of a sulphonyl sulfonium salt photoacid generator synthesized from patchouli alcohol as claimed in any of claims 1-2 in a lithographic material.
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| CN112645849A (en) * | 2020-12-23 | 2021-04-13 | 上海博栋化学科技有限公司 | Sulfonium sulfonate photo-acid generator synthesized from abietic acid and synthetic method thereof |
| CN112645951A (en) * | 2020-12-23 | 2021-04-13 | 上海博栋化学科技有限公司 | Sulfonium sulfonate photo-acid generator synthesized from vinblastine and synthetic method thereof |
| CN112661805A (en) * | 2020-12-23 | 2021-04-16 | 上海博栋化学科技有限公司 | Sulfonium salt photo-acid generator synthesized from Bromus buxus alkali B and preparation method thereof |
| CN112679499A (en) * | 2020-12-23 | 2021-04-20 | 上海博栋化学科技有限公司 | Sulfonium sulfonate photo-acid generator synthesized from matrine and synthesis method thereof |
| CN114380722A (en) * | 2021-12-30 | 2022-04-22 | 宁波南大光电材料有限公司 | Rapid hydrolysis method of sulfonyl fluoride alkane ester |
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| CN112645849A (en) * | 2020-12-23 | 2021-04-13 | 上海博栋化学科技有限公司 | Sulfonium sulfonate photo-acid generator synthesized from abietic acid and synthetic method thereof |
| CN112645951A (en) * | 2020-12-23 | 2021-04-13 | 上海博栋化学科技有限公司 | Sulfonium sulfonate photo-acid generator synthesized from vinblastine and synthetic method thereof |
| CN112661805A (en) * | 2020-12-23 | 2021-04-16 | 上海博栋化学科技有限公司 | Sulfonium salt photo-acid generator synthesized from Bromus buxus alkali B and preparation method thereof |
| CN112679499A (en) * | 2020-12-23 | 2021-04-20 | 上海博栋化学科技有限公司 | Sulfonium sulfonate photo-acid generator synthesized from matrine and synthesis method thereof |
| CN114380722A (en) * | 2021-12-30 | 2022-04-22 | 宁波南大光电材料有限公司 | Rapid hydrolysis method of sulfonyl fluoride alkane ester |
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