CN113429293A - Degradable resin monomer synthesized from 2-cyclopentyl cyclopentanone and preparation method and application thereof - Google Patents
Degradable resin monomer synthesized from 2-cyclopentyl cyclopentanone and preparation method and application thereof Download PDFInfo
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- CN113429293A CN113429293A CN202110700758.6A CN202110700758A CN113429293A CN 113429293 A CN113429293 A CN 113429293A CN 202110700758 A CN202110700758 A CN 202110700758A CN 113429293 A CN113429293 A CN 113429293A
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- resin monomer
- degradable resin
- photoresist
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- cyclopentyl
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- 239000011347 resin Substances 0.000 title claims abstract description 39
- 229920005989 resin Polymers 0.000 title claims abstract description 39
- 239000000178 monomer Substances 0.000 title claims abstract description 38
- CWZGKTMWPFTJCS-UHFFFAOYSA-N 2-cyclopentylcyclopentan-1-one Chemical compound O=C1CCCC1C1CCCC1 CWZGKTMWPFTJCS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000004404 heteroalkyl group Chemical group 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 125000006239 protecting group Chemical group 0.000 claims description 6
- 239000007818 Grignard reagent Substances 0.000 claims description 3
- -1 acrylic acid compound Chemical class 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 150000004795 grignard reagents Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000001259 photo etching Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 239000012043 crude product Substances 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 4
- 238000005530 etching Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 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 2
- 239000012267 brine Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 2
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- C—CHEMISTRY; METALLURGY
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of photoresist, and discloses a degradable resin monomer synthesized by 2-cyclopentyl cyclopentanone, a preparation method and application thereof, wherein the structural general formula of the degradable resin monomer is as follows:
Description
Technical Field
The invention relates to the technical field of photoresist, in particular to a degradable resin monomer synthesized by 2-cyclopentyl cyclopentanone, a preparation method and application 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 main components of the photoresist material are resin, photoacid generator, and corresponding additives and solvents, and the material has chemical sensitivity with light (including visible light, ultraviolet light, electron beam, etc.) and changes its solubility in developer through photochemical reaction. According to the difference of photochemical reaction mechanism, the photoresist is divided into a positive photoresist and a negative photoresist: after exposure, the solubility of the photoresist in a developing solution is increased, and the photoresist with the same pattern as that of the mask is obtained and is called as a positive photoresist; after exposure, the photoresist has reduced solubility or even no solubility in a developing solution, and a negative photoresist with a pattern opposite to that of the mask is obtained.
The existing resin monomer has low etching resistance, and the solubility of the photoresist in a developing solution is insufficient after exposure, so that a degradable resin monomer synthesized by 2-cyclopentyl cyclopentanone and a preparation method thereof are provided.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a degradable resin monomer synthesized by 2-cyclopentyl cyclopentanone, and a preparation method and application thereof.
The invention provides the following technical scheme: a degradable resin monomer synthesized by 2-cyclopentyl cyclopentanone, wherein the degradable resin monomer has the following structural general formula:
wherein R is alkyl or heteroalkyl.
Preferably, the degradable resin monomer is selected from the following structures:
The preparation method of the degradable resin monomer synthesized from 2-cyclopentyl cyclopentanone comprises the following specific synthetic route:
wherein R is alkyl or heteroalkyl, and R' is a protecting group.
The method comprises the following synthetic steps:
s1, protecting hydroxyl of the raw material I by a protecting group to obtain an intermediate II;
s2, 2-cyclopentyl cyclopentanone is reduced under the condition of a Grignard reagent formed by the intermediate II and metal to obtain an intermediate III containing a hydroxyl;
s3, deprotecting the intermediate III to obtain an intermediate IV containing two hydroxyl groups;
and S4, carrying out esterification reaction on the intermediate IV and an acrylic acid compound to obtain a degradable resin monomer V.
Preferably, in S1, the hydroxyl group of the raw material I is protected by benzyl or silyl ether to obtain an intermediate II.
Preferably, the starting material i is selected in particular from the following structures:
or
The degradable resin monomer synthesized from 2-cyclopentyl cyclopentanone is used for preparing the photoresist.
Compared with the prior art, the degradable resin monomer synthesized by 2-cyclopentyl cyclopentanone and the preparation method thereof have the following beneficial effects:
(1) the degradable resin monomer contains a tert-butyl structure, the photoacid generator can generate acid during exposure, the tert-butyl structure can be broken under the action of the acid, so that a polymerization main chain is broken, small segments are formed, the edge roughness of a photoetching pattern can be improved, the resolution of the photoresist is improved, and meanwhile, hydroxyl with good alkali solubility is formed after the tert-butyl structure is broken, so that the dissolution in the developing process is facilitated, the dissolution speed of the photoresist in a developing solution after exposure is increased, and the contrast of the photoresist is increased;
(2) the annular structure of the 2-cyclopentyl cyclopentanone also greatly increases the etching resistance of the photoresist, and the polyester-based structure of the resin monomer also increases the solubility of the resin monomer in a fat-soluble solvent, so that the spin coating is convenient and uniform;
(3) the invention has simple synthetic route and convenient operation.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present disclosure clearer and to describe more fully technical solutions of the embodiments of the present disclosure, and to keep the following description of the embodiments of the present disclosure clear and concise, detailed descriptions of known functions and known parts of the disclosure are omitted so as to avoid unnecessarily obscuring the concepts of the present disclosure.
A degradable resin monomer synthesized by 2-cyclopentyl cyclopentanone, wherein the degradable resin monomer has the following structural general formula:
wherein R is alkyl or heteroalkyl.
The degradable resin monomer has the following structure:
A preparation method of a degradable resin monomer synthesized from 2-cyclopentyl cyclopentanone comprises the following specific synthetic route:
wherein R is alkyl or heteroalkyl, and R' is a protecting group.
The method comprises the following synthetic steps:
s1, protecting hydroxyl of the raw material I by a protecting group to obtain an intermediate II;
s2, 2-cyclopentyl cyclopentanone is reduced under the condition of a Grignard reagent formed by the intermediate II and metal to obtain an intermediate III containing a hydroxyl;
s3, deprotecting the intermediate III to obtain an intermediate IV containing two hydroxyl groups;
and S4, carrying out esterification reaction on the intermediate IV and an acrylic compound to obtain a resin monomer V.
In S1, hydroxyl of the raw material I is protected by benzyl or silyl ether to obtain an intermediate II.
The starting material I specifically comprises a structure selected from:
or
Example 1
Preparation of Compounds 1-2:
tert-butyldimethylsilyl chloride (13g, 86.3mmol) was dissolved in tetrahydrofuran (50g), and the above mixture was added dropwise to tetrahydrofuran (100g) containing 2-bromoethanol 1-1(10g, 80.0mmol) under nitrogen protection at 0 ℃ and stirred for 3 hours. The resulting suspension was filtered to obtain a filtrate, the filtrate was concentrated, and compound 1-2(15g, 62.7mmol, molar yield 78.4%) was purified by distillation under reduced pressure.
Preparation of Compounds 1-3:
compound 1-2(15g, 62.7mmol) was dissolved in diethyl ether (100g), and the above mixture was added dropwise to diethyl ether (30g) containing magnesium (1.5g,62.5mmol) under nitrogen, and stirred at 25 ℃ for 1 hour. 2-Cyclopentylcyclopentanone (9g, 59.1mmol) was dissolved in diethyl ether (80g), added dropwise to the above mixture, and stirred for 3 hours. The reaction was quenched, then filtered, the filtrate was extracted with ethyl acetate, the resulting organic layers were combined, washed with brine, dried over anhydrous sodium sulfate, and concentrated to give a crude product. The crude product was recrystallized from ethyl acetate and hexane to give compound 1-3(15.5g, 49.6mmol, 83.9% molar yield).
Preparation of Compounds 1-4:
a1 Mol/L tetrahydrofuran solution of tetrabutylammonium fluoride (54mL, 54mmol) was added dropwise to tetrahydrofuran (100g) containing compound 1-3(15.5g, 49.6mmol) at 25 ℃ under nitrogen, and stirred for 3 hours. The reaction was quenched with saturated ammonium chloride solution, extracted with ethyl acetate, and the combined organic phases were concentrated to give a crude product which was purified by silica gel column to give compounds 1-4(8.5g, 42.9mmol, 86.4% molar yield).
Preparation of degradable resin monomers 1-5:
compounds 1-4(8.5g, 42.9mmol), triethylamine (9g, 88.9mmol) were dissolved in dichloromethane (150g), methacryloyl chloride (9g, 86.1mmol) was added dropwise to the mixture, stirred at 0 ℃ under nitrogen for 30 minutes, and then stirred at room temperature for 4 hours. Filtering, concentrating the filtrate to obtain crude product, and purifying the crude product by column chromatography to obtain degradable resin monomer 1-5(12g, 35.9mmol, molar yield 83.7%).
Example 2
Preparation of Compound 2-2:
tert-butyldimethylchlorosilane (10g, 66.3mmol) was dissolved in tetrahydrofuran (50g), and the above mixture was dropwise added to tetrahydrofuran (100g) containing 3-bromomethyl-3-hydroxymethyl-1-oxetane 2-1(10g, 55.2mmol) under nitrogen protection at 0 ℃ and stirred for 3 hours. The resulting suspension was filtered to obtain a filtrate, the filtrate was concentrated, and compound 2-2(13.5g, 45.7mmol, molar yield 82.8%) was purified by distillation under reduced pressure.
Preparation of Compounds 2-3:
compound 2-2(13.5g, 45.7mmol) was dissolved in diethyl ether (100g), and the above mixture was added dropwise to diethyl ether (30g) containing magnesium (1.2g,50mmol) under nitrogen atmosphere, and stirred at 25 ℃ for 1 hour. 2-Cyclopentylcyclopentanone (7g, 46.0mmol) was dissolved in diethyl ether (80g), and the solution was added dropwise to the mixture and stirred for 3 hours. The reaction was quenched, then filtered, the filtrate was extracted with ethyl acetate, the resulting organic layers were combined, washed with brine, dried over anhydrous sodium sulfate, and concentrated to give a crude product. The crude product was recrystallized from ethyl acetate and hexane to give compound 2-3(13.5g, 36.6mmol, 79.6% molar yield).
Preparation of Compounds 2-4:
a1 Mol/L tetrahydrofuran solution (38mL, 38mmol) of tetrabutylammonium fluoride was added dropwise to 100g of tetrahydrofuran containing 2-3(13.5g, 36.6mmol) under nitrogen protection at 25 ℃ and stirred for 3 hours. The reaction solution was quenched with saturated ammonium chloride solution, extracted with ethyl acetate, the combined organic phases were concentrated to give a crude product, which was purified by silica gel column to give compound 2-4(8g, 31.5mmol, 85.9% molar yield).
Preparation of degradable resin monomer 2-5:
compound 2-4(8g, 31.5mmol), triethylamine (7g, 69.2mmol) were dissolved in dichloromethane (150g), methacryloyl chloride (7g, 67.0mmol) was added dropwise to the above mixture, stirred at 0 ℃ under nitrogen for 30 minutes, and then stirred at room temperature for 4 hours. Filtering, concentrating the filtrate to obtain crude product, and purifying the crude product by column chromatography to obtain degradable resin monomer 2-5(9.5g, 24.3mmol, molar yield 77.4%).
The above embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and the scope of the present invention is defined by the claims. Various modifications and equivalents may be made by those skilled in the art within the spirit and scope of the present invention, and such modifications and equivalents should also be considered as falling within the scope of the present invention.
Claims (6)
1. A degradable resin monomer synthesized by 2-cyclopentyl cyclopentanone is characterized in that the structural general formula of the degradable resin monomer is as follows:
wherein R is alkyl or heteroalkyl.
2. The degradable resin monomer synthesized from 2-cyclopentyl cyclopentanone of claim 1, wherein the degradable resin monomer is selected from the following structures:
3. A preparation method of a degradable resin monomer synthesized from 2-cyclopentyl cyclopentanone is characterized in that the synthetic route of the degradable resin monomer is as follows:
wherein R is alkyl or heteroalkyl, and R' is a protecting group.
The method comprises the following synthetic steps:
s1, protecting hydroxyl of the raw material I by a protecting group to obtain an intermediate II;
s2, 2-cyclopentyl cyclopentanone is reduced under the condition of a Grignard reagent formed by the intermediate II and metal to obtain an intermediate III containing a hydroxyl;
s3, deprotecting the intermediate III to obtain an intermediate IV containing two hydroxyl groups;
and S4, carrying out esterification reaction on the intermediate IV and an acrylic acid compound to obtain a degradable resin monomer V.
4. The method for preparing the degradable resin monomer synthesized from 2-cyclopentyl cyclopentanone according to claim 3, wherein: in S1, hydroxyl of the raw material I is protected by benzyl or silyl ether to obtain an intermediate II.
5. The method for preparing the degradable resin monomer synthesized from 2-cyclopentyl cyclopentanone according to claim 3, wherein: the raw material I is specifically selected from the following structures:
6. The use of the degradable resin monomer synthesized from 2-cyclopentyl cyclopentanone according to any of claims 1-2 in the preparation of a photoresist.
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|---|---|---|---|---|
| WO2004042477A1 (en) * | 2002-11-04 | 2004-05-21 | Dongjin Semichem Co., Ltd. | Chemically amplified polymer having pendant group with dicyclohexyl and resist composition comprising the same |
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2021
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004042477A1 (en) * | 2002-11-04 | 2004-05-21 | Dongjin Semichem Co., Ltd. | Chemically amplified polymer having pendant group with dicyclohexyl and resist composition comprising the same |
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