CN111056980A - Sulfonium salt photo-acid generator containing guaiacol structure and preparation method thereof - Google Patents
Sulfonium salt photo-acid generator containing guaiacol structure and preparation method thereof Download PDFInfo
- Publication number
- CN111056980A CN111056980A CN201911373768.2A CN201911373768A CN111056980A CN 111056980 A CN111056980 A CN 111056980A CN 201911373768 A CN201911373768 A CN 201911373768A CN 111056980 A CN111056980 A CN 111056980A
- Authority
- CN
- China
- Prior art keywords
- sulfonium salt
- guaiacol
- sulfonium
- photoacid generator
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical group COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000002253 acid Substances 0.000 title abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 8
- -1 sulfonium halide Chemical class 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 150000001450 anions Chemical class 0.000 claims abstract description 11
- 150000001768 cations Chemical class 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 4
- 229960001867 guaiacol Drugs 0.000 claims abstract description 4
- 125000004404 heteroalkyl group Chemical group 0.000 claims abstract description 4
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims abstract description 3
- TWVJWDMOZJXUID-SDDRHHMPSA-N Guaiol Chemical compound C1([C@H](CC[C@H](C2)C(C)(C)O)C)=C2[C@@H](C)CC1 TWVJWDMOZJXUID-SDDRHHMPSA-N 0.000 claims description 7
- TWVJWDMOZJXUID-QJPTWQEYSA-N guaiol Natural products OC(C)(C)[C@H]1CC=2[C@H](C)CCC=2[C@@H](C)CC1 TWVJWDMOZJXUID-QJPTWQEYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 125000001538 guaiol group Chemical group 0.000 claims description 3
- VMJFYMAHEGJHFH-UHFFFAOYSA-M triphenylsulfanium;bromide Chemical compound [Br-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 VMJFYMAHEGJHFH-UHFFFAOYSA-M 0.000 claims description 3
- ZFEAYIKULRXTAR-UHFFFAOYSA-M triphenylsulfanium;chloride Chemical compound [Cl-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 ZFEAYIKULRXTAR-UHFFFAOYSA-M 0.000 claims description 3
- ILMKIFUAABITSV-UHFFFAOYSA-M tris(4-methylphenyl)sulfanium;bromide Chemical compound [Br-].C1=CC(C)=CC=C1[S+](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ILMKIFUAABITSV-UHFFFAOYSA-M 0.000 claims description 3
- GDXHNOZSKQKGCT-UHFFFAOYSA-M tris(4-methylphenyl)sulfanium;chloride Chemical compound [Cl-].C1=CC(C)=CC=C1[S+](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 GDXHNOZSKQKGCT-UHFFFAOYSA-M 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000007805 chemical reaction reactant Substances 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 239000003999 initiator Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 24
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010009 beating Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WXHBENUYPQJFIG-UHFFFAOYSA-N OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.N Chemical class OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.N WXHBENUYPQJFIG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- STUDWPIFXGYVRW-UHFFFAOYSA-N ethyl 2-bromo-2-cyclopentylacetate Chemical compound BrC(C(=O)OCC)C1CCCC1 STUDWPIFXGYVRW-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- XSQIGJCTPAJWQT-UHFFFAOYSA-M sodium;1,1-difluoro-2-hydroxy-2-oxoethanesulfonate Chemical compound [Na+].OS(=O)(=O)C(F)(F)C([O-])=O XSQIGJCTPAJWQT-UHFFFAOYSA-M 0.000 description 1
- LZKVGVXWGQWLAI-UHFFFAOYSA-M sodium;1,1-difluoro-2-hydroxyethanesulfonate Chemical compound [Na+].OCC(F)(F)S([O-])(=O)=O LZKVGVXWGQWLAI-UHFFFAOYSA-M 0.000 description 1
- SMKZBQZAMSKHNS-UHFFFAOYSA-M sodium;2-sulfoacetate Chemical compound [Na+].OS(=O)(=O)CC([O-])=O SMKZBQZAMSKHNS-UHFFFAOYSA-M 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/26—All rings being cycloaliphatic the ring system containing ten carbon atoms
Abstract
The invention relates to the technical field of photoresist, and particularly discloses a sulfonium salt type photoacid generator containing a guaiacol structure and a preparation method thereof, wherein the photoacid generator comprises anions and cations, and the anions and the cations respectively have the following structures:
wherein R represents alkyl, cycloalkyl, heteroalkyl or heterocycloalkyl, P1、P2And P3Each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 12 carbon atoms. The photoacid generator prepared by the invention has good hydrophilicity, can improve the solubility in an organic solvent, and can effectively inhibit the diffusion of acid. The invention also provides a preparation method of the sulfonium salt photo-acid generator, which takes guaiacol as a reaction initiator to react with the photo-acid generatorThe sulfonium halide is reacted to obtain the sulfonium salt compound, and the preparation method is simple.
Description
Technical Field
The invention relates to the technical field of photoresist, in particular to a sulfonium salt photo-acid generator containing a guaiacol structure and a preparation method thereof.
Background
The photoacid generator is also called as photoacid generator, is a light-sensitive compound, is decomposed under illumination to generate acid, and the generated acid can enable acid-sensitive resin to generate decomposition or crosslinking reaction, so that the dissolution contrast of an illuminated part and a non-illuminated part in a developing solution is increased, and the photoacid generator can be used in the technical field of pattern micro-processing.
Among them, photoacid generators are widely used in imaging systems such as chemically amplified resists (also known as photoresists). Commonly used photoacid generators include diazonium salt compounds, onium salt compounds, nitrogen hydroxysulfonate compounds, and the like. Among them, onium salt compounds are very important photoacid generating systems. Currently, sulfonium salts and iodonium salts are important. The sulfonium salt and the iodonium salt have low production cost and mature process and are commercialized in large batch. Because the onium salt photo-acid generator counter anion is super strong base anion, the proton acid generated after photolysis is super strong acid, and the method is stable, non-volatile, small in diffusion range and widely applicable to chemical amplification resists.
The chemically amplified resist is widely applied to integrated circuits, and the development of large-scale and super-large-scale integrated circuits in recent years greatly promotes the research, development and application of photoresist, and along with the gradual reduction of the feature size of the integrated circuits, the influence of edge roughness is more and more obvious, and the type of the photoacid generator is also developed forward. However, the conventional onium salt type photoacid generators still have a problem of diffusion of acid, and thus edge roughness cannot be reduced.
Disclosure of Invention
The invention aims to provide a sulfonium salt photo-acid generator containing a guaiacol structure and a preparation method thereof, so as to solve the problem that the existing onium salt photo-acid generators in the background technology still have acid diffusion.
In order to achieve the purpose, the invention provides the following technical scheme:
a sulfonium salt photo-acid generator containing guaiol structure comprises anion and cation, the structure of the anion is shown as the following formula:
R represents alkyl, cycloalkyl, heteroalkyl or heterocycloalkyl; and the methylene group in the alkyl, cycloalkyl, heteroalkyl or heterocycloalkyl group may be substituted with an ester group, a carbonate group and a difluoromethylene group;
the structure of the cation is shown as the following formula:
P1、P2And P3Each independently represents a hydrogen atom or an optionally substituted alkyl group having 1 to 12 carbon atoms.
As a further scheme of the invention: the anion comprises any one of the following structural formulas:
the preparation method of the sulfonium salt type photoacid generator containing the guaiacol structure comprises the following steps:
taking guaiol as a reaction starting material, and introducing a sulfonic group through reaction to obtain a sulfonate compound containing a guaiol structure;
and carrying out ion exchange reaction on the sulfonate compound containing the guaiacol structure and halogenated sulfonium, and sequentially recrystallizing, filtering and drying reaction liquid to obtain the sulfonium salt photo-acid generator.
As a still further scheme of the invention: the guaiol has the structure shown as follows:
as a still further scheme of the invention: the sulfonium halide is any one of triphenylsulfonium bromide, triphenylsulfonium chloride, tris (4-methylphenyl) sulfonium chloride or tris (4-methylphenyl) sulfonium bromide.
Compared with the prior art, the invention has the beneficial effects that:
1) the sulfonium salt compound prepared by the invention has good hydrophilic-lipophilic balance, and meanwhile, the synthesis process is simple, the operation is convenient, and the synthesis route is few.
2) The sulfonium salt photo-acid generator provided by the invention contains a guaiacol structure, further contains anions including a guaiacol structure and an ester group structure, has a relatively large molecular weight, can inhibit the diffusion of the sulfonium salt photo-acid generator and reduce the edge roughness of a photoresist; meanwhile, the ester group structure contained in the photo-acid generator can increase the lipid solubility of the photo-acid generator in resin and solvent to form photoresist which is dissolved uniformly, imaging is facilitated, the sulfonium salt photo-acid generator has certain hydrophilicity and can be well adhered to a silicon wafer, the problem that the existing onium salt photo-acid generator still has acid diffusion is solved, edge roughness can be reduced, and resolution is improved.
3) The invention takes guaiol as raw material, and guaiol is a green natural product, is pollution-free, simple and easy to obtain, and has wide market prospect.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
A sulfonium salt photo-acid generator 1-3 comprises the following specific synthetic steps:
1) guaiol 1-1(45.0mmol, 10g), sodium difluorosulfoacetate (45.4mmol, 9g) and p-toluenesulfonic acid monohydrate (5.2mmol, 1g) were added to toluene (100g), heated under reflux for 18 hours and cooled to room temperature to give a mixture; filtering the mixture to obtain a solid, said solid being washed three times with acetonitrile; the mixed acetonitrile solution was concentrated and added to methyl t-butyl ether for beating, the above mixed solution was filtered, and the filter cake was collected and dried to obtain 1-2(31.1mmol, 12.5g, yield 69.2%) of the sulfonate compound containing the guaiacol structure.
2) Dissolving the sulfonate compound 1-2(29.8mmol, 12g) containing the guaiacol structure obtained in the step 1) and triphenylsulfonium bromide (30.0mmol, 10.3g) in a mixed solvent of dichloromethane (60g) and water (60 g); the mixture was stirred at 30 ℃ for 24 hours; the reaction solution was washed with deionized water (30g × 4), and the organic solvent was evaporated to dryness, after which the obtained residue was dissolved in dichloromethane and added to methyl tert-butyl ether for recrystallization; the recrystallized solid was vacuum filtered, washed with methyl tert-butyl ether and vacuum dried to give an off-white solid (28.0mmol, 18g, yield 93.9%) which was a photoacid generator 1-3.
Specifically, the synthetic route from step 1) to step 2) is as follows:
example 2
A sulfonium salt photo-acid generator 2-3 is specifically synthesized by the following steps:
1) guaiol 2-1(45.0mmol, 10g), 2-sulfoacetate sodium salt (45.0mmol, 7.3g) and p-toluenesulfonic acid monohydrate (5.2mmol, 1g) were added to toluene (100g), heated under reflux for 18 hours and cooled to room temperature; the mixture was filtered to give a solid, which was washed three times with acetonitrile; the mixed acetonitrile solution was concentrated and added to methyl t-butyl ether for beating, the above mixed solution was filtered, and the oven-dried cake was collected to obtain the sulfonate compound 2-2 containing the guaiacol structure (33.3mmol, 12.2g, 74.0%).
2) Dissolving the sulfonate compound 2-2(32.7mmol, 12g) containing the guaiacol structure obtained in the step 1) and tris (4-methylphenyl) sulfonium chloride (32.9mmol, 11.2g) in a mixed solvent of dichloromethane (80g) and water (80 g); the mixture was stirred at 30 ℃ for 24 hours; the reaction solution was washed with deionized water (40g × 4), and the organic solvent was evaporated to dryness, after which the obtained residue was dissolved in dichloromethane and added to methyl tert-butyl ether for recrystallization; the recrystallized solid was vacuum filtered, washed with methyl tert-butyl ether and vacuum dried to give an off-white solid (30.8mmol, 20g, yield 94.1%) which was the photoacid generator 2-3.
Specifically, the synthetic route from step 1) to step 2) is as follows:
example 3
3-3 of a sulfonium salt photo-acid generator, which comprises the following specific synthetic steps:
1) pyridine (11.4mmol, 9g), bis (trichloromethyl) carbonate (15.2mmol, 4.5g) was added to dichloromethane (400g) with stirring at 0 ℃ under nitrogen, followed by slow addition of guaiacol 3-1(44.5mmol, 10 g); the reaction mixture was stirred at 25 ℃ for 3 hours; then 1, 1-difluoro-2-hydroxy-ethanesulfonic acid sodium salt (45.1mmol, 8.3g) was added to the reaction solution, stirred for 10 hours; concentrating by rotary evaporation to obtain a mixture, filtering the mixture to obtain a solid, and washing the solid with acetonitrile for three times; the mixed acetonitrile solution was concentrated and added to methyl t-butyl ether for beating, the mixture was filtered, and the dried cake was collected to obtain the sulfonate compound 3-2 containing the guaiacol structure (34.7mmol, 15g, yield 77.1%).
2) Dissolving the sulfonate compound 3-2(27.7mmol, 12g) containing the guaiacol structure obtained in the step 1) and triphenylsulfonium chloride (27.8mmol, 8.3g) in a mixed solvent of dichloromethane (50g) and water (50 g); the mixture was stirred at 30 ℃ for 4 hours; the reaction solution was washed with deionized water (30g × 4), and the organic solvent was evaporated to dryness, after which the obtained residue was dissolved in dichloromethane and added to methyl tert-butyl ether for recrystallization; the recrystallized solid was vacuum filtered, washed with methyl tert-butyl ether and vacuum dried to give an off-white solid (25.4mmol, 17.1g, 91.6% yield) which was 3-3% of the photoacid generator.
Specifically, the synthetic route from step 1) to step 2) is as follows:
example 4
A sulfonium salt photo-acid generator 4-5 is specifically synthesized by the following steps:
1) sodium hydride (66.7mmol, 1.6g) was slowly added to a mixture of guaiacol 4-1(45.0mmol, 10g) and tetrahydrofuran (100g) at 0 ℃ under nitrogen, and stirred for 20 minutes; then, ethyl 2-bromo-2-cyclopentylacetate (45.1mmol, 10.6g) was added dropwise to the above mixed solution, and stirred for 20 minutes; then mixing and stirring for 6 hours at 25 ℃; after the reaction is finished, adding water for quenching at 0 ℃; the quenched mixture was concentrated by rotary evaporation and extracted with dichloromethane (70g × 3); mixing the extractive solutions, washing with saturated saline solution (200g), drying with anhydrous sodium sulfate, and concentrating by rotary evaporation to obtain crude product; the crude product was purified by column chromatography to give the first liquid compound 4-2(37.2mmol, 14g, yield 82.7%).
2) Adding the first liquid compound 4-2(31.9mmol, 12g) obtained in step 1) and sodium hydroxide (47.5mol, 1.9g) to a mixture of water (5g) and methanol (80g), and stirring at 25 ℃ for 24 hours; concentrating the reaction solution, and adjusting the pH value of the solution to 2 by using hydrochloric acid to obtain a mixed solution; the resulting mixture was extracted with ethyl acetate (100g × 2), the combined extracts were washed with saturated brine (200g), dried over anhydrous sodium sulfate, and concentrated by rotary evaporation to give 4-3(30.1mmol10.5g, yield 94.5%) of a second liquid compound.
3) Adding the second liquid compound 4-3(28.7mmol, 10g) obtained in step 2), 1-difluoro-2-hydroxy-ethanesulfonic acid sodium salt (28.8mol, 5.3g) and p-toluenesulfonic acid monohydrate (5.2mmol, 1g) to toluene (90g), heating under reflux for 18 hours and cooling to room temperature; the mixture was filtered to give a solid, which was washed three times with acetonitrile; the mixed acetonitrile solution was concentrated and added to methyl t-butyl ether for slurrying, the mixture was filtered, and the dried cake was collected to obtain the first solid compound 4-4(21.4mmol, 11g, yield 74.5%).
4) Dissolving the first solid compound 4-4(19.4mmol, 10g) and tris (4-methylphenyl) sulfonium bromide (19.5mmol, 7.5g) obtained in step 3) in a mixed solvent of dichloromethane (60g) and water (60 g); the mixture was stirred at 30 ℃ for 24 hours; the reaction solution was washed with deionized water (50g × 4), and the organic solvent was evaporated to dryness, after which the obtained residue was dissolved in dichloromethane and added to methyl tert-butyl ether for recrystallization; the recrystallized solid was vacuum filtered, washed with methyl tert-butyl ether and vacuum dried to give an off-white solid (17.6mmol, 14g, yield 90.4%) which was 4-5% of the photoacid generator.
Specifically, the synthetic route from step 1) to step 4) is as follows:
while the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (5)
1. A sulfonium salt type photoacid generator containing a guaiacol structure, which comprises an anion and a cation, wherein the structure of the anion is shown as the following formula:
R represents alkyl, cycloalkyl, heteroalkyl or heterocycloalkyl;
the structure of the cation is shown as the following formula:
P1、P2And P3Respectively independent earth surfaceRepresents a hydrogen atom or an optionally substituted alkyl group having 1 to 12 carbon atoms.
2. The sulfonium salt photoacid generator containing a guaiacol structure of claim 1, wherein the anion comprises any one of the following structural formulas:
3. a method for producing a photoacid generator of the sulfonium salt type containing a guaiacol structure as described in any of claims 1 to 2, comprising the steps of:
taking guaiol as a reaction starting material, and introducing a sulfonic group through reaction to obtain a sulfonate compound containing a guaiol structure;
and carrying out ion exchange reaction on the sulfonate compound containing the guaiacol structure and halogenated sulfonium, and sequentially recrystallizing, filtering and drying reaction liquid to obtain the sulfonium salt compound.
4. The method for producing a sulfonium salt photoacid generator containing a guaiacol structure as claimed in claim 3, wherein the guaiacol has a structure represented by the following formula:
5. the method for producing a sulfonium salt-based photoacid generator containing a guaiacol structure as claimed in claim 3, wherein the sulfonium halide is any one of triphenylsulfonium bromide, triphenylsulfonium chloride, tris (4-methylphenyl) sulfonium chloride or tris (4-methylphenyl) sulfonium bromide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911373768.2A CN111056980A (en) | 2019-12-25 | 2019-12-25 | Sulfonium salt photo-acid generator containing guaiacol structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911373768.2A CN111056980A (en) | 2019-12-25 | 2019-12-25 | Sulfonium salt photo-acid generator containing guaiacol structure and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111056980A true CN111056980A (en) | 2020-04-24 |
Family
ID=70302757
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911373768.2A Pending CN111056980A (en) | 2019-12-25 | 2019-12-25 | Sulfonium salt photo-acid generator containing guaiacol structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111056980A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112114495A (en) * | 2020-10-23 | 2020-12-22 | 华衍化学(上海)有限公司 | Fluorine-free photoacid generator and preparation method thereof |
| CN112552298A (en) * | 2020-12-23 | 2021-03-26 | 上海博栋化学科技有限公司 | Sulfonium salt photo-acid generator synthesized from 16-epi-NB-methyl Voacarpine base and preparation method thereof |
| CN112631072A (en) * | 2020-12-23 | 2021-04-09 | 上海博栋化学科技有限公司 | Sulfonium salt photo-acid generator synthesized from 10-hydroxy climbing mountain orange alkali and preparation method thereof |
| 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 |
| CN112661756A (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 20-hydroxyduraline and preparation 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 |
| CN112679514A (en) * | 2020-12-23 | 2021-04-20 | 上海博栋化学科技有限公司 | Sulfonium salt photo-acid generator synthesized from papaya alkali and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010120923A (en) * | 2008-05-08 | 2010-06-03 | Tokyo Ohka Kogyo Co Ltd | Resist composition, resist pattern-forming method, new compound, and acid generator |
| CN102067041A (en) * | 2008-06-16 | 2011-05-18 | 住友化学株式会社 | Method of resist treatment |
| CN102089715A (en) * | 2008-07-10 | 2011-06-08 | 住友化学株式会社 | Method of resist treatment |
| JP2012008500A (en) * | 2010-06-28 | 2012-01-12 | Fujifilm Corp | Pattern forming method, chemically amplified resist composition, and resist film |
| JP2012234038A (en) * | 2011-04-28 | 2012-11-29 | Fujifilm Corp | Active ray-sensitive or radiation-sensitive resin composition, and resist film and pattern forming method using the composition |
-
2019
- 2019-12-25 CN CN201911373768.2A patent/CN111056980A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010120923A (en) * | 2008-05-08 | 2010-06-03 | Tokyo Ohka Kogyo Co Ltd | Resist composition, resist pattern-forming method, new compound, and acid generator |
| CN102067041A (en) * | 2008-06-16 | 2011-05-18 | 住友化学株式会社 | Method of resist treatment |
| CN102089715A (en) * | 2008-07-10 | 2011-06-08 | 住友化学株式会社 | Method of resist treatment |
| JP2012008500A (en) * | 2010-06-28 | 2012-01-12 | Fujifilm Corp | Pattern forming method, chemically amplified resist composition, and resist film |
| JP2012234038A (en) * | 2011-04-28 | 2012-11-29 | Fujifilm Corp | Active ray-sensitive or radiation-sensitive resin composition, and resist film and pattern forming method using the composition |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112114495A (en) * | 2020-10-23 | 2020-12-22 | 华衍化学(上海)有限公司 | Fluorine-free photoacid generator and preparation method thereof |
| CN112552298A (en) * | 2020-12-23 | 2021-03-26 | 上海博栋化学科技有限公司 | Sulfonium salt photo-acid generator synthesized from 16-epi-NB-methyl Voacarpine base and preparation method thereof |
| CN112631072A (en) * | 2020-12-23 | 2021-04-09 | 上海博栋化学科技有限公司 | Sulfonium salt photo-acid generator synthesized from 10-hydroxy climbing mountain orange alkali and preparation method thereof |
| 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 |
| CN112661756A (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 20-hydroxyduraline and preparation 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 |
| CN112679514A (en) * | 2020-12-23 | 2021-04-20 | 上海博栋化学科技有限公司 | Sulfonium salt photo-acid generator synthesized from papaya alkali and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111056980A (en) | Sulfonium salt photo-acid generator containing guaiacol structure and preparation method thereof | |
| CN111138331A (en) | Sulfonium salt photo-acid generator containing β -eucalyptol structure and preparation method thereof | |
| CN111077731A (en) | Sulfonium salt photo-acid generator containing trumpet-shaped tea alcohol structure and preparation method thereof | |
| CN111116426A (en) | Sulfonium salt photo-acid generator containing patchouli alcohol structure and preparation method thereof | |
| CN111123645A (en) | Sulfonium salt photo-acid generator containing cedrol structure and preparation method thereof | |
| EP2093213B1 (en) | Positive resist composition and method of forming a resist pattern using the same | |
| KR101839155B1 (en) | Resist composition, method of forming resist pattern, novel compound, and acid generator | |
| KR101720352B1 (en) | Resist composition and method of forming resist pattern | |
| KR20110131904A (en) | Photoacid generator, mathod for manufacturing the same and resist composition comprising the same | |
| CN111138405A (en) | Sulfonium sulfonate photo-acid generator synthesized from patchouli alcohol and synthesis method thereof | |
| CN111138407A (en) | Sulfonium sulfonate photo-acid generator synthesized from trumpet-shaped tea alcohol and synthesis method thereof | |
| CN111138408A (en) | Sulfonium sulfonate photo-acid generator synthesized from cedrol and synthesis method thereof | |
| JP2012022212A (en) | Resist composition, method for forming resist pattern, novel compound and acid generator | |
| CN111138406A (en) | Sulfonium sulfonate photo-acid generator synthesized from guaiol and synthesis method thereof | |
| CN112679499A (en) | Sulfonium sulfonate photo-acid generator synthesized from matrine and synthesis method thereof | |
| TWI445691B (en) | Sulfonium compound, photo-acid generator, and method for manufacturing the same | |
| CN112661755A (en) | Sulfonium salt photo-acid generator synthesized from isocorynanthine and preparation method thereof | |
| CN112920099A (en) | Photoacid generator with diphenyl sulfonium structure and synthesis method thereof | |
| CN112679514A (en) | Sulfonium salt photo-acid generator synthesized from papaya alkali and preparation method thereof | |
| CN112631072A (en) | Sulfonium salt photo-acid generator synthesized from 10-hydroxy climbing mountain orange alkali and preparation method thereof | |
| CN112661756A (en) | Sulfonium salt photo-acid generator synthesized from 20-hydroxyduraline and preparation method thereof | |
| CN111138288A (en) | Photoresist resin monomer containing five-membered ring β -ketone structure and synthetic method thereof | |
| CN111072482A (en) | Photoresist resin monomer synthesized from spiro [2.5] decane-6, 8-dione and synthesis method thereof | |
| CN112552298A (en) | Sulfonium salt photo-acid generator synthesized from 16-epi-NB-methyl Voacarpine base and preparation method thereof | |
| CN111056945A (en) | Photoresist resin monomer synthesized from spiro [5.5] undecane-3, 9-dione and synthesis method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200424 |