CN111138287A - Photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -diketone and synthetic method thereof - Google Patents
Photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -diketone and synthetic method thereof Download PDFInfo
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- CN111138287A CN111138287A CN201911373996.XA CN201911373996A CN111138287A CN 111138287 A CN111138287 A CN 111138287A CN 201911373996 A CN201911373996 A CN 201911373996A CN 111138287 A CN111138287 A CN 111138287A
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- indene
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- 229920005989 resin Polymers 0.000 title claims abstract description 66
- 239000011347 resin Substances 0.000 title claims abstract description 66
- 239000000178 monomer Substances 0.000 title claims abstract description 59
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 45
- 238000010189 synthetic method Methods 0.000 title description 3
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 13
- -1 alkyl Grignard reagent Chemical class 0.000 claims abstract description 13
- 238000003747 Grignard reaction Methods 0.000 claims abstract description 11
- 238000005886 esterification reaction Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 8
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 4
- 150000001924 cycloalkanes Chemical class 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- ZNPBIUPPEFUWIT-UHFFFAOYSA-N 3a,4,5,6,7,7a-hexahydroindene-1,3-dione Chemical compound C1CCCC2C(=O)CC(=O)C21 ZNPBIUPPEFUWIT-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000001259 photo etching Methods 0.000 abstract description 4
- 239000002952 polymeric resin Substances 0.000 abstract description 4
- 229920003002 synthetic resin Polymers 0.000 abstract description 4
- 238000005530 etching Methods 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 72
- 238000006243 chemical reaction Methods 0.000 description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000012074 organic phase Substances 0.000 description 24
- 239000012043 crude product Substances 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 239000005457 ice water Substances 0.000 description 11
- 238000009835 boiling Methods 0.000 description 9
- 239000012295 chemical reaction liquid Substances 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical class [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- MMYKTRPLXXWLBC-UHFFFAOYSA-N 1-bromo-2-ethoxyethane Chemical compound CCOCCBr MMYKTRPLXXWLBC-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- JRQAAYVLPPGEHT-UHFFFAOYSA-N 2-bromoethylcyclohexane Chemical compound BrCCC1CCCCC1 JRQAAYVLPPGEHT-UHFFFAOYSA-N 0.000 description 2
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- RIEJARKPVINFOD-UHFFFAOYSA-N 2-bromoethoxycyclohexane Chemical compound BrCCOC1CCCCC1 RIEJARKPVINFOD-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AQNQQHJNRPDOQV-UHFFFAOYSA-N bromocyclohexane Chemical compound BrC1CCCCC1 AQNQQHJNRPDOQV-UHFFFAOYSA-N 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002170 ethers Chemical group 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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- 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
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- 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
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -diketone and a synthesis method thereof, belonging to the technical field of chemical synthesis and photoetching. The structural general formula of the photoresist resin monomer is shown as formula I:
in the formula I, R1Is a saturated alkane or cycloalkane, R2Is hydrogen or methyl, and the synthesis method comprises the following steps: under the protection of inert gas, hexahydro-1H-indene-1, 3(2H) -diketone and alkyl Grignard reagent or cycloalkyl Grignard reagent are subjected to Grignard reaction, and water is added after the Grignard reaction is finishedQuenching, and carrying out post-treatment and purification to obtain an intermediate; and (3) carrying out esterification reaction on the intermediate and acryloyl chloride or methacryloyl chloride, and after the esterification reaction is finished, carrying out post-treatment and purification to obtain the resin monomer. The resin monomer provided by the invention is a degradable resin monomer, and the polymer resin containing the resin monomer has better etching resistance and can improve the resolution of photoresist photoetching patterns.
Description
Technical Field
The invention relates to the technical field of chemical synthesis and photoetching, in particular to a photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -diketone 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 main components of the photoresist are resin, photoacid generator, and corresponding additives and solvents, and these materials have chemical sensitivity with light (including visible light, ultraviolet light, electron beam, etc.) and undergo a photochemical reaction to change their solubility in a developing solution. 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 resin used by the photoresist is a polymer formed by copolymerizing a plurality of resin monomers, wherein the acid-sensitive resin monomer is an important component for realizing the dissolution difference of the resin in a developing solution before and after exposure, the common acid-sensitive resin monomer only has one acid-sensitive group, the polymer resin is linear, the solubility difference between an exposed area and an unexposed area is formed by deprotection after the exposure of the acid-sensitive group, and the main chain of the linear polymer cannot be broken. Therefore, the existing photoresist has the problem of lower resolution of the photoetching pattern due to the specific structure of the acid-sensitive resin monomer.
Disclosure of Invention
An object of an embodiment of the present invention is to provide a photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -dione to solve the problems set forth in the background art.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
a photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -diketone, wherein the structural general formula of the resin monomer is shown as a formula I:
in the formula I, R1Is a saturated alkane or cycloalkane, R2Is hydrogen or methyl.
As a preferred embodiment of the present invention, the structural formula of the resin monomer is one of formula II, formula III, formula IV, formula V, formula VI and formula VII:
another object of an embodiment of the present invention is to provide a method for synthesizing the resin monomer, which includes the following steps:
placing hexahydro-1H-indene-1, 3(2H) -diketone and alkyl Grignard reagent or cycloalkyl Grignard reagent in a first solvent for Grignard reaction under the protection of inert gas, adding water for quenching after the Grignard reaction is finished, and carrying out aftertreatment and purification to obtain an intermediate;
and (3) placing the intermediate and acryloyl chloride or methacryloyl chloride in a second solvent for esterification, and after the esterification is finished, carrying out post-treatment and purification to obtain the resin monomer.
As another preferable scheme of the embodiment of the invention, the temperature of the Grignard reaction is 0-30 ℃; the temperature of the esterification reaction is 0-70 ℃.
As another preferable mode of the embodiment of the present invention, the first solvent is dehydrated ether.
As another preferable mode of the embodiment of the present invention, the second solvent is one of anhydrous tetrahydrofuran, toluene and chloroform.
As another preferable scheme of the embodiment of the present invention, triethylamine or pyridine is added to the second solvent.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
the embodiment of the invention provides a novel photoresist resin monomer which is a degradable resin monomer, the photoresist resin monomer is synthesized by hexahydro-1H-indene-1, 3(2H) -diketone and contains two unsaturated carbon-carbon double bonds, so that crosslinking can be generated in the process of polymerizing the monomer with other resin monomers to form a three-dimensional network-structured polymerized resin, so that the polymerized resin has better etching resistance, during exposure, a photoacid generator generates acid, in an exposure area, a (methyl) acrylate on a main chain is broken under an acidic condition, the main chain of the polymer resin is broken to generate a product with smaller molecular weight, the solubility of the exposed resin in a developing solution is increased, and the difference of the dissolving speeds of the polymer resin before and after exposure in the developing solution is increased, so that the edge roughness of a developed pattern is improved, the resolution of the photoresist pattern is greatly improved.
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.
The embodiment of the invention provides a photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -diketone, wherein the structural general formula of the resin monomer is shown as a formula I:
in the formula I, R1Is a saturated alkane or cycloalkane, R2Is hydrogen or methyl.
The reaction route of the synthetic method of the photoresist resin monomer is as follows:
the method specifically comprises the following steps:
s1, under the protection of inert gas, putting hexahydro-1H-indene-1, 3(2H) -diketone (structural formula is shown in formula VIII) and alkyl Grignard reagent or cycloalkyl Grignard reagent into a first solvent for Grignard reaction, adding water for quenching after the Grignard reaction is finished, and carrying out aftertreatment purification to obtain an intermediate (structural formula is shown in formula IX); wherein the temperature of the Grignard reaction is 0-30 ℃, and the first solvent is anhydrous ether.
S2, placing the intermediate and acryloyl chloride or methacryloyl chloride in a second solvent for esterification, and after the esterification is finished, carrying out post-treatment and purification to obtain the resin monomer (the structural formula is shown in formula I); wherein the temperature of the esterification reaction is 0-70 ℃, and the second solvent is one of anhydrous tetrahydrofuran, toluene and chloroform; in addition, triethylamine or pyridine may be added to the second solvent.
The resin can be prepared by polymerizing and crosslinking the resin monomer with other resin monomers, and the photoresist can be prepared by mixing the resin with components such as a photoacid generator, an additive, a solvent and the like. In addition, the following examples can be referred to for the specific embodiment of the method for synthesizing the resin monomer in practical application.
Example 1
This example provides a photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -dione, the reaction scheme of the synthesis method of the photoresist resin monomer is as follows:
the method specifically comprises the following steps:
s1, preparation of methyl Grignard reagent: adding 3.2g of magnesium chips (132mmol) into 15ml of anhydrous ether, and adding one iodine tablet to obtain a reaction solution; then, 12.5g of methyl bromide (132mmol) was dissolved in 25mL of diethyl ether to prepare a methyl bromoethyl ether solution; and then, under the protection of nitrogen, firstly adding 6mL of methyl ethyl bromide solution into the reaction solution, after 5 minutes, slightly boiling the reaction solution, continuously dropwise adding the rest of methyl ethyl bromide solution while stirring, supplementing 20mL of ethyl ether, heating to keep slightly boiling, and refluxing for half an hour to obtain the methyl Grignard reagent.
S2, synthesis of intermediate (formula 1-2): under the protection of nitrogen, cooling the prepared methyl Grignard reagent with ice water, dropwise adding an ether (20mL) solution of hexahydro-1H-indene-1, 3(2H) -diketone (formula 1-1, 10.0g and 66mmol) while stirring, controlling the dropwise adding speed, keeping the reaction liquid slightly boiling, after dropwise adding, continuously stirring at room temperature for half an hour to separate out white solid in the reaction liquid, cooling the reaction liquid to 0 ℃ with ice water, slowly dropwise adding 20mL of 20% dilute sulfuric acid, after dropwise adding, separating an ether layer, extracting an aqueous phase with ethyl acetate for three times, wherein the amount of ethyl acetate extracted each time is 100mL, combining organic phases, purifying and drying a crude product obtained after concentrating the organic phase by column chromatography to obtain 10.5g of an intermediate (57mmol), wherein the yield is 86.7%.
S3, dissolving 10.5g of the intermediate in 120mL of anhydrous tetrahydrofuran, and adding 23.6g of triethylamine (233 mmol); then, cooling to 0 ℃ with ice water, and slowly dropwise adding an anhydrous tetrahydrofuran (50mL) solution of acryloyl chloride (10.4g, 115mmol) under the protection of nitrogen to obtain a reaction solution; after the reaction solution is heated to room temperature and continuously reacts for 5 hours, the reaction solution is placed under vacuum to be concentrated to remove the solvent, 50mL of ethyl acetate and 20mL of saturated sodium bicarbonate water solution are added, the organic phase is separated, the water phase is extracted for three times by using ethyl acetate, the using amount of the ethyl acetate extracted each time is 80mL, the organic phases are combined, the organic phase is washed by using saturated saline solution and dried by using anhydrous sodium sulfate to obtain a crude product, the crude product is purified by column chromatography and dried to obtain 14.2g of resin monomer (formula 1-3, 49mmol), and the yield is 85.2%.
Example 2
This example provides a photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -dione, the reaction scheme of the synthesis method of the photoresist resin monomer is as follows:
the method specifically comprises the following steps:
s1, following steps S1 to S2 of example 1 above, 10.2g of intermediate (formula 2-2, 55mmol) was obtained with a yield of 84.2%.
S2, dissolving 10.2g of the intermediate in 120mL of anhydrous tetrahydrofuran, and adding 22.4g of triethylamine (221 mmol); then, cooling to 0 ℃ with ice water, and slowly dropwise adding a solution of methacryloyl chloride (11.6g, 111mmol) in anhydrous tetrahydrofuran (50mL) under the protection of nitrogen to obtain a reaction solution; after the reaction solution is heated to room temperature and continuously reacts for 5 hours, the reaction solution is placed under vacuum to be concentrated to remove the solvent, 50mL of ethyl acetate and 20mL of saturated sodium bicarbonate water solution are added, the organic phase is separated, the water phase is extracted for three times by using ethyl acetate, the using amount of the ethyl acetate extracted each time is 80mL, the organic phases are combined, the organic phase is washed by using saturated saline solution and dried by using anhydrous sodium sulfate to obtain a crude product, the crude product is purified by column chromatography and dried to obtain 15.6g of resin monomer (formula 2-3, 49mmol), and the yield is 88%.
Example 3
This example provides a photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -dione, the reaction scheme of the synthesis method of the photoresist resin monomer is as follows:
the method specifically comprises the following steps:
s1, preparing an ethyl format reagent: adding 3.2g of magnesium chips (132mmol) into 15ml of anhydrous ether, and adding one iodine tablet to obtain a reaction solution; then, 14.4g of ethyl bromide (132mmol) was dissolved in 25mL of diethyl ether to prepare an ethyl bromoethyl ether solution; and then, under the protection of nitrogen, firstly adding 6mL of ethyl bromoethyl ether solution into the reaction solution, after 5 minutes, slightly boiling the reaction solution, continuously dropwise adding the rest of ethyl bromoethyl ether solution while stirring, supplementing 20mL of ethyl ether, heating to keep slightly boiling, and refluxing for half an hour to obtain the ethyl Grignard reagent.
S2, synthesis of intermediate (formula 3-2): under the protection of nitrogen, cooling the prepared ethyl Grignard reagent with ice water, dropwise adding an ether (20mL) solution of hexahydro-1H-indene-1, 3(2H) -dione (formula 3-1, 10.0g and 66mmol) while stirring, controlling the dropwise adding speed, keeping the reaction liquid slightly boiling, after dropwise adding, continuously stirring at room temperature for half an hour to separate out white solid in the reaction liquid, controlling the temperature of the reaction liquid at 30 ℃, slowly dropwise adding 20mL of 20% dilute sulfuric acid, after dropwise adding, separating an ether layer, extracting an aqueous phase with ethyl acetate for three times, wherein the amount of ethyl acetate extracted each time is 100mL, combining organic phases, purifying and drying a crude product obtained after concentrating the organic phase by column chromatography to obtain 11.5g of an intermediate (54mmol), wherein the yield is 82.4%.
S3, dissolving 11.5g of the intermediate in 120mL of anhydrous tetrahydrofuran, and adding 22g of triethylamine (217 mmol); then, cooling to 0 ℃ with ice water, and slowly dropping a solution of acryloyl chloride (9.9g, 109mmol) in anhydrous tetrahydrofuran (50mL) under the protection of nitrogen to obtain a reaction solution; after the reaction solution is heated to room temperature and continuously reacts for 5 hours, the reaction solution is placed under vacuum to be concentrated to remove the solvent, 50mL of ethyl acetate and 20mL of saturated sodium bicarbonate water solution are added, the organic phase is separated, the water phase is extracted for three times by using ethyl acetate, the using amount of the ethyl acetate extracted each time is 80mL, the organic phases are combined, the organic phase is washed by using saturated saline solution and dried by using anhydrous sodium sulfate to obtain a crude product, the crude product is purified by column chromatography and dried to obtain 14.8g of resin monomer (formula 3-3, 46mmol), and the yield is 85.3%.
Example 4
This example provides a photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -dione, the reaction scheme of the synthesis method of the photoresist resin monomer is as follows:
the method specifically comprises the following steps:
s1, following steps S1 to S2 of example 3 above, 11.3g of intermediate (formula 4-2, 53mmol) was obtained with a yield of 81%.
S2, dissolving 11.3g of the intermediate in 120mL of chloroform, and adding 21.6g of triethylamine (213 mmol); then, cooling to 0 ℃ with ice water, and slowly dropping a chloroform (50mL) solution of methacryloyl chloride (11.2g, 107mmol) under the protection of nitrogen to obtain a reaction solution; after the reaction solution is heated to room temperature and continuously reacts for 5 hours, the reaction solution is placed under vacuum to be concentrated to remove the solvent, 50mL of ethyl acetate and 20mL of saturated sodium bicarbonate water solution are added, the organic phase is separated, the water phase is extracted for three times by using ethyl acetate, the using amount of the ethyl acetate extracted each time is 80mL, the organic phases are combined, the organic phase is washed by using saturated saline solution and dried by using anhydrous sodium sulfate to obtain a crude product, the crude product is purified by column chromatography and dried to obtain 16.3g of resin monomer (formula 4-3, 47mmol), and the yield is 88%.
Example 5
This example provides a photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -dione, the reaction scheme of the synthesis method of the photoresist resin monomer is as follows:
the method specifically comprises the following steps:
s1, preparation of cyclohexyl formatted reagent: adding 3.2g of magnesium chips (132mmol) into 15ml of anhydrous ether, and adding one iodine tablet to obtain a reaction solution; then, 21.5g of cyclohexyl bromide (132mmol) was dissolved in 25mL of diethyl ether to prepare a cyclohexyl bromoethyl ether solution; and then, under the protection of nitrogen, firstly adding 6mL of cyclohexyl ethyl bromide solution into the reaction solution, after 5 minutes, slightly boiling the reaction solution, continuously dropwise adding the rest of cyclohexyl ethyl bromide solution while stirring, supplementing 20mL of ethyl ether, heating to keep slightly boiling, and refluxing for half an hour to obtain the cyclohexyl-form reagent.
S2, synthesis intermediate (formula 5-2): under the protection of nitrogen, cooling the prepared cyclohexyl form reagent with ice water, dropwise adding an ether (20mL) solution of hexahydro-1H-indene-1, 3(2H) -diketone (formula 5-1, 10.0g and 66mmol) while stirring, controlling the dropwise adding speed, keeping the reaction liquid slightly boiling, after dropwise adding, continuously stirring at room temperature for half an hour to separate out white solid in the reaction liquid, cooling the reaction liquid to 0 ℃ with ice water, slowly dropwise adding 20mL of 20% dilute sulfuric acid, after dropwise adding, separating an ether layer, extracting an aqueous phase with ethyl acetate for three times, wherein the amount of ethyl acetate extracted each time is 100mL, combining organic phases, purifying a crude product obtained after organic phase column chromatography concentration, and drying to obtain 17g of an intermediate (53mmol), wherein the yield is 80.7%.
S3, dissolving 17g of the intermediate in 120mL of toluene, and adding 16.8g of pyridine (212 mmol); then, cooling to 0 ℃ with ice water, and slowly dropping a toluene (50mL) solution of acryloyl chloride (9.7g, 107mmol) under the protection of nitrogen to obtain a reaction solution; after the reaction solution is heated to room temperature and continuously reacts for 5 hours, the reaction solution is placed under vacuum to be concentrated to remove the solvent, 50mL of ethyl acetate and 20mL of saturated sodium bicarbonate water solution are added, the organic phase is separated, the water phase is extracted for three times by using ethyl acetate, the using amount of the ethyl acetate extracted each time is 80mL, the organic phases are combined, the organic phase is washed by using saturated saline solution and dried by using anhydrous sodium sulfate to obtain a crude product, the crude product is purified by column chromatography and dried to obtain 17.6g of resin monomer (formula 5-3, 41mmol), and the yield is 77.4%.
Example 6
This example provides a photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -dione, the reaction scheme of the synthesis method of the photoresist resin monomer is as follows:
the method specifically comprises the following steps:
s1, following steps S1 to S2 of example 5 above, 17.2g of intermediate (formula 6-2, 54mmol) was obtained with a yield of 81.7%.
S2, dissolving 17.2g of the intermediate in 120mL of anhydrous tetrahydrofuran, and adding 21.8g of triethylamine (215 mmol); then, cooling to 0 ℃ with ice water, and slowly dropwise adding a solution of methacryloyl chloride (11.3g, 108mmol) in anhydrous tetrahydrofuran (50mL) under the protection of nitrogen to obtain a reaction solution; after the reaction solution is heated to room temperature and continuously reacts for 5 hours, the reaction solution is placed under vacuum to be concentrated to remove the solvent, 50mL of ethyl acetate and 20mL of saturated sodium bicarbonate water solution are added, the organic phase is separated, the water phase is extracted for three times by using ethyl acetate, the using amount of the ethyl acetate extracted each time is 80mL, the organic phases are combined, the organic phase is washed by using saturated saline solution and dried by using anhydrous sodium sulfate to obtain a crude product, the crude product is purified by column chromatography and dried to obtain 18.8g of resin monomer (formula 6-3, 41mmol), and the yield is 76.7%.
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 (7)
1. A photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -diketone is characterized in that the structural general formula of the resin monomer is shown as a formula I:
in the formula I, R1Is a saturated alkane or cycloalkane, R2Is hydrogen or methyl.
2. The photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -dione as claimed in claim 1, wherein the structural formula of the resin monomer is one of formula II, formula III, formula IV, formula V, formula VI and formula VII:
3. a method of synthesizing the monomer of the photoresist resin synthesized from hexahydro-1H-indene-1, 3(2H) -dione as claimed in claim 1 or 2, comprising the steps of:
placing hexahydro-1H-indene-1, 3(2H) -diketone and alkyl Grignard reagent or cycloalkyl Grignard reagent in a first solvent for Grignard reaction under the protection of inert gas, adding water for quenching after the Grignard reaction is finished, and carrying out aftertreatment and purification to obtain an intermediate;
and (3) placing the intermediate and acryloyl chloride or methacryloyl chloride in a second solvent for esterification, and after the esterification is finished, carrying out post-treatment and purification to obtain the resin monomer.
4. The method for synthesizing the photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -diketone according to claim 3, wherein the temperature of the Grignard reaction is 0-30 ℃; the temperature of the esterification reaction is 0-70 ℃.
5. The method for synthesizing the photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -diketone according to claim 3, wherein the first solvent is dehydrated ether.
6. The method for synthesizing the photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -dione as claimed in claim 3, wherein the second solvent is one of anhydrous tetrahydrofuran, toluene and chloroform.
7. The method for synthesizing the photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -dione as claimed in claim 3 or 6, wherein triethylamine or pyridine is added to the second solvent.
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| CN111777587A (en) * | 2020-06-18 | 2020-10-16 | 徐州博康信息化学品有限公司 | Degradable photoresist resin monomer synthesized from oxaspiro [4.5] decanedione and synthesis method thereof |
| CN111777583A (en) * | 2020-06-18 | 2020-10-16 | 徐州博康信息化学品有限公司 | Degradable photoresist resin monomer synthesized from pyran-3, 5-dione and synthesis method thereof |
| CN111777579A (en) * | 2020-06-18 | 2020-10-16 | 徐州博康信息化学品有限公司 | Degradable photoresist resin monomer synthesized from furandione and synthesis method thereof |
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| WO2019065526A1 (en) * | 2017-09-26 | 2019-04-04 | 富士フイルム株式会社 | Composition for forming underlayer film for imprinting, kit, curable composition for imprinting, laminated body, method for manufacturing laminated body, method for manufacturing cured product pattern, and method for manufacturing circuit substrate |
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| CN111777583A (en) * | 2020-06-18 | 2020-10-16 | 徐州博康信息化学品有限公司 | Degradable photoresist resin monomer synthesized from pyran-3, 5-dione and synthesis method thereof |
| CN111777579A (en) * | 2020-06-18 | 2020-10-16 | 徐州博康信息化学品有限公司 | Degradable photoresist resin monomer synthesized from furandione and synthesis method thereof |
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