CN114380688A - Preparation method of acid-sensitive photoresist resin monomer - Google Patents
Preparation method of acid-sensitive photoresist resin monomer Download PDFInfo
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- CN114380688A CN114380688A CN202111632855.2A CN202111632855A CN114380688A CN 114380688 A CN114380688 A CN 114380688A CN 202111632855 A CN202111632855 A CN 202111632855A CN 114380688 A CN114380688 A CN 114380688A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000011347 resin Substances 0.000 title claims abstract description 21
- 229920005989 resin Polymers 0.000 title claims abstract description 21
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 19
- 239000002253 acid Substances 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 38
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 18
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 18
- 238000004321 preservation Methods 0.000 claims abstract description 17
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims abstract description 10
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000012074 organic phase Substances 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical group ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 239000012071 phase Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000012043 crude product Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 230000000977 initiatory effect Effects 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- -1 methyl halide Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 230000001502 supplementing effect Effects 0.000 claims description 4
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- 239000002274 desiccant Substances 0.000 claims description 3
- 229940102396 methyl bromide Drugs 0.000 claims description 3
- 229940050176 methyl chloride Drugs 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 230000003321 amplification Effects 0.000 abstract description 3
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000002952 polymeric resin Substances 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of an acid-sensitive photoresist resin monomer, which comprises the following steps: b) mixing the compound III with tetrahydrofuran, dripping a Grignard reagent at the temperature of-15 to-20 ℃, and carrying out heat preservation reaction; c) and then, dropwise adding a compound II, carrying out heat preservation reaction at 10-15 ℃, and purifying to obtain the acid-sensitive photoresist resin monomer I. The preparation method disclosed by the invention is mild in reaction conditions, suitable for amplification reaction and high in purity of the obtained product.
Description
Technical Field
The invention relates to the technical field of 193nm photoresist, in particular to a preparation method of an acid-sensitive photoresist resin monomer.
Background
The 193nm photoresist is basically a chemically amplified resist, which is a photoresist based on the principle of chemical amplification and mainly comprises a polymer resin, a photoacid generator, and corresponding additives (alkaline additives, dissolution inhibitors, etc.) and a solvent. Among them, the polymer resin is formed by copolymerization between resin monomers having different side chain structures, which are key components for imparting desired functions to the polymer resin, and usually provides the polymer resin with a polar group and an acid-sensitive group. The polar group can balance the hydrophilicity and hydrophobicity of the resin, improve the adhesion between the resin and the substrate, and provide developability for the host resin. The acid sensitive group can be separated from the side chain under the action of a photoacid generator, so that the resin is converted from insoluble to alkali-soluble, and the solubility contrast of the exposed region and the unexposed region is realized.
The poly (methyl) acrylate system is a resin polymer widely applied to 193nm photoresist, but the existing (methyl) acrylate resin monomer is difficult to prepare and purify.
Disclosure of Invention
The present invention is directed to a method for preparing an acid-sensitive photoresist resin monomer, which overcomes the above-mentioned drawbacks of the prior art.
In order to achieve the object of the present invention, the present application provides the following technical solutions.
The application provides a preparation method of an acid-sensitive photoresist resin monomer, which is characterized in that the reaction of the preparation method comprises the following synthetic route:
wherein R is1Is alkyl, R2Is a hydrogen atom or an alkyl group; preferably, R1Is C1-C6 alkyl, R2Is a hydrogen atom or a C1-C6 alkyl group, and the preparation method specifically comprises the following steps:
b) mixing the compound III with tetrahydrofuran, dripping a Grignard reagent into the mixture at the temperature of between 15 ℃ below zero and 20 ℃ below zero, and carrying out heat preservation reaction;
c) and then, dropwise adding a compound II, carrying out heat preservation reaction at 10-15 ℃, and purifying to obtain the acid-sensitive photoresist resin monomer I.
In one embodiment, the preparation method further comprises at least one of the following technical features:
b1) in the step b), the molar ratio of the compound III to the Grignard reagent is 1: 1-1: 4;
b2) in the step b), the reaction time is kept for 1-5 hours.
In one embodiment, the preparation method further comprises at least one of the following technical features:
c1) in the step c), the molar ratio of the compound III to the compound II is 1: 1-1: 4;
c2) in the step c), the time of the heat preservation reaction is 12-24 hours.
In one embodiment, the purification in step c) comprises the steps of:
d) adding a hydrochloric acid aqueous solution into the reaction liquid obtained after the heat preservation reaction in the step c), and stirring to obtain a first water phase and a first organic phase;
e) adding ethyl acetate into the first water phase for extraction to obtain a second water phase and a second organic phase; continuously adding ethyl acetate into the second water phase for extraction to obtain a third water phase and a third organic phase;
f) combining the first organic phase, the second organic phase and the third organic phase, and obtaining a crude product after alkali washing, salt washing, drying, reduced pressure concentration and distillation;
g) and rectifying the crude product.
In one embodiment, the preparation method further comprises at least one of the following technical features:
d1) in the step d), the concentration of the hydrochloric acid is 0.5-2 mol/L;
d2) the volume ratio of the addition amount of the hydrochloric acid aqueous solution to the reaction solution obtained after the heat preservation reaction is 1: (2-5).
In one embodiment, the preparation method further comprises at least one of the following technical features:
f1) in the step f), the alkali liquor used for alkali washing is a NaOH solution with the mass concentration of 5%; the number of the alkaline washing is at least 2;
f2) in step f), the raw material for the salt is a saturated NaCl solution;
f3) in step f), the drying agent used for drying is anhydrous sodium sulfate or anhydrous magnesium sulfate;
f4) in the step f), the temperature for the reduced pressure concentration is 30-35 ℃, and the pressure is 10-15 mmHg;
f5) in the step f), the distillation temperature is 40-50 ℃, and the distillation time is 4-6 hours.
In one embodiment, the preparation method further comprises the following technical features:
g1) in the step g), the rectification adopts segmented rectification, and fractions at the top of the tower with the external temperature of 85-90 ℃ and the top temperature of 68-72 ℃ are collected.
In one embodiment of the first aspect, the preparation method further comprises the preparation of a grignard reagent, the preparation of the grignard reagent comprising the steps of:
a) and (3) initiating a reaction between the magnesium chips and tetrahydrofuran in an inert environment, supplementing the tetrahydrofuran after a period of time, and then introducing methyl halide until the magnesium chips completely react to obtain the Grignard reagent.
In one embodiment of the first aspect, the preparation method further comprises the following features:
a1) the molar ratio of the magnesium chips to the chloroalkane is 1: 2-1: 4;
a2) the methyl halide is selected from methyl chloride or methyl bromide;
a3) the temperature of the initiation reaction is 20-30 ℃, and the time of the initiation reaction is 0.5-1 hour;
a4) the inert environment is a nitrogen environment.
Compared with the prior art, the invention has the beneficial effects that: the preparation method has mild reaction conditions, is suitable for amplification reaction, and the obtained product has high purity.
Drawings
FIG. 1 is a GC spectrum of the main fraction of the product obtained in example 1.
Detailed Description
Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are incorporated herein by reference in their entirety and their equivalent family patents are also incorporated by reference, especially as they disclose definitions relating to synthetic techniques, products and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
The numerical ranges in this application are approximations, and thus may include values outside of the ranges unless otherwise specified. A numerical range includes all numbers from the lower value to the upper value, in increments of 1 unit, provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if a component, physical or other property (e.g., molecular weight, etc.) is recited as 100 to 1000, it is intended that all individual values, e.g., 100, 101,102, etc., and all subranges, e.g., 100 to 166,155 to 170,198 to 200, etc., are explicitly recited. For ranges containing a numerical value less than 1 or containing a fraction greater than 1 (e.g., 1.1, 1.5, etc.), then 1 unit is considered appropriate to be 0.0001, 0.001, 0.01, or 0.1. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is typically considered 0.1. These are merely specific examples of what is intended to be expressed and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application. It should also be noted that the terms "first," "second," and the like herein do not define a sequential order, but merely distinguish between different structures.
When used with respect to chemical compounds, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively) unless expressly specified otherwise. In addition, unless explicitly stated otherwise, the use of the terms "a", "an" or "the" are intended to include the plural forms thereof.
The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not intended to exclude the presence of other elements, steps or procedures not expressly disclosed herein. To the extent that any doubt is eliminated, all compositions herein containing, including, or having the term "comprise" may contain any additional additive, adjuvant, or compound, unless expressly stated otherwise. Rather, the term "consisting essentially of … …" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, except those necessary for performance. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.
A method for preparing acid-sensitive photoresist resin monomer,
wherein R is1Is alkyl, R2Is a hydrogen atom or an alkyl group; the preparation method comprises the following steps:
b) mixing the compound III with tetrahydrofuran, dripping a Grignard reagent at the temperature of-15 to-20 ℃, and carrying out heat preservation reaction; for example, the Grignard reagent is added dropwise at-16 deg.C, 18 deg.C, etc
c) Then, dropwise adding a compound II, carrying out heat preservation reaction at 10-15 ℃, and purifying to obtain an acid-sensitive photoresist resin monomer I; for example, the reaction is carried out at the temperature of 12 ℃ and 14 ℃.
In one embodiment, the preparation method further comprises at least one of the following technical features:
b1) in the step b), the molar ratio of the compound III to the Grignard reagent is 1: 1-1: 4; such as 1:1, 1:2, 1:3, 1:4, etc.
b2) In the step b), the reaction time is kept for 1-5 hours, such as 2 hours and 4 hours.
In one embodiment, the preparation method further comprises the following features:
c1) in the step c), the molar ratio of the compound III to the compound II is 1: 1-1: 4; such as 1:1, 1:2, 1:3, 1:4, etc.
c2) In the step c), the reaction time is kept for 12-24 hours, such as 15 hours and 18 hours.
In one embodiment, the purification in step c) comprises the steps of:
d) adding a hydrochloric acid aqueous solution into the reaction liquid obtained after the heat preservation reaction in the step c), and stirring to obtain a first water phase and a first organic phase;
e) adding ethyl acetate into the first water phase for extraction to obtain a second water phase and a second organic phase; continuously adding ethyl acetate into the second water phase for extraction to obtain a third water phase and a third organic phase;
f) combining the first organic phase, the second organic phase and the third organic phase, and obtaining a crude product after alkali washing, salt washing, drying, reduced pressure concentration and distillation;
g) and rectifying the crude product.
In one embodiment, the preparation method further comprises at least one of the following technical features:
d1) in the step d), the concentration of the hydrochloric acid aqueous solution is 0.5-2 mol/L, such as 1mol/L, 1.5mol/L and the like;
d2) the volume ratio of the addition amount of the hydrochloric acid aqueous solution to the reaction liquid obtained after the heat preservation reaction is 1: 2-5.
In one embodiment of the first aspect, the preparation method further comprises the following features:
f1) in the step f), the alkali liquor used for alkali washing is a NaOH solution with the mass concentration of 5%; the number of the alkaline washing is at least 2;
f2) in step f), the raw material used for salt washing is washed by saturated NaCl solution;
f3) in step f), the drying agent used for drying is selected from anhydrous sodium sulfate or anhydrous magnesium sulfate;
f4) in the step f), the temperature for the reduced pressure concentration is 30-35 ℃, such as 32 ℃, 34 ℃ and the like, and the pressure is 10-15 mmHg, such as 12mmHg, 14mmHg and the like;
f5) in the step f), the distillation temperature is 40-50 ℃, such as 43 ℃, 45 ℃, 48 ℃ and the like, and the distillation time is 4-6 hours, such as 5 hours and the like.
In one embodiment, the preparation method further comprises the following features:
g1) in the step g), the rectification adopts segmented rectification, and fractions at the top of the tower with the external temperature of 85-90 ℃ and the top temperature of 68-72 ℃ are collected.
In one embodiment, the preparation method further comprises the preparation of a format reagent, the preparation of the format reagent comprising the steps of:
a) and (3) initiating a reaction between the magnesium chips and tetrahydrofuran in an inert environment, supplementing the tetrahydrofuran, and then introducing methyl halide until the magnesium chips are completely reacted to obtain the Grignard reagent.
In an embodiment of the first aspect, the preparation method further comprises at least one of the following technical features:
a1) the molar ratio of the magnesium chips to the methyl halide is 1: 2-1: 4;
a2) the methyl halide is selected from methyl chloride or methyl bromide;
a3) the temperature of the initiation reaction is 20-30 ℃, and the time of the initiation reaction is 0.5-1 hour;
a4) the inert environment is a nitrogen environment.
Examples
The following will describe in detail the embodiments of the present invention, which are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and the specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.
Example 1
1. Adding 440g of magnesium chips and 2kg of tetrahydrofuran into a 10L reaction bottle at 25 ℃ under the anhydrous and oxygen-free conditions of nitrogen protection to initiate reaction, wherein 5kg of tetrahydrofuran is added (the system is gray black) after the initiation reaction is carried out for 0.5 hour, then introducing chloromethane gas, keeping the ventilation quantity and continuously reacting until no magnesium chips exist, introducing the chloromethane gas at 2743.2g, and keeping the temperature at room temperature for later use under the nitrogen protection.
2. Adding 3, 3-dimethyl-2-butanone (600g) and 2.66kg (3L) tetrahydrofuran into a 20L reaction bottle, cooling to a temperature below-15 ℃, starting to slowly dropwise add the Grignard reagent (dropwise adding while maintaining the temperature of-15 ℃), preserving heat after dropwise adding for 2 hours, controlling the raw material content to be less than 5%, starting to dropwise add acrylic anhydride (2266.3g) while maintaining the temperature at 10 ℃, preserving heat after dropwise adding for 24 hours, carrying out post-treatment, pouring the reaction solution into 10L of 0.5mol/L hydrochloric acid aqueous solution, stirring and layering, extracting the aqueous phase for 2 times by using 3L ethyl acetate, and combining the organic phases; washing with 5% sodium hydroxide water solution 3L/time for 2 times, then washing with 3L saturated saline for 1 time, drying organic phase anhydrous sodium sulfate, concentrating under reduced pressure at 30-35 deg.C and 10-15 mmHg to obtain brown yellow crude product 1.67kg, and rapidly distilling under pressure to obtain colorless transparent crude product 680g, GC 75.5%.
3. And (3) rectification: distilling the colorless and transparent crude product with 30CM glass packed column by using a common water pump,
collecting 166g of front cut (external temperature 40-80 ℃, top temperature 40-68 ℃) and ensuring that GC is 86.5%;
450g of main fraction (external temperature 85-90 ℃, top temperature 68-72 ℃) was collected, and the yield was 44.2% when GC was 98.36%.
Example 2
1. At 23 ℃, 488g of magnesium chips and 2kg of tetrahydrofuran are added into a 10L reaction bottle under the condition of nitrogen protection, water and oxygen free to initiate reaction, 5kg of tetrahydrofuran is added (the system is gray black) to initiate reaction for 1 hour, then chloromethane gas is introduced, the introduction amount of the chloromethane gas is 4056.6g, the ventilation amount is maintained to continuously react until no magnesium chips exist, and the mixture is kept at room temperature for standby by nitrogen protection.
2. Adding 3, 3-dimethyl-2-butanone (670g) and 2.66kg (3L) tetrahydrofuran into a 20L reaction bottle, cooling to-20 ℃, slowly dropwise adding the Grignard reagent (dropwise adding while maintaining-20 ℃), keeping the temperature for 2 hours after dropwise adding, controlling the temperature of 1 percent of raw materials to be less than 5 ℃, keeping the temperature for 15 ℃, dropwise adding acrylic anhydride (2522.2g), keeping the temperature for 15 ℃ for 12 hours after dropwise adding, carrying out post-treatment on reaction liquid, pouring the reaction liquid into 10L 2mol/L hydrochloric acid aqueous solution, stirring and layering, extracting an aqueous phase for 2 times by using 3L ethyl acetate, combining organic phases, washing the organic phases for 2 times by using 5 percent sodium hydroxide aqueous solution for 3L/time, then washing the organic phases for 1 time by using 3L saturated salt, drying the organic phases by using anhydrous sodium sulfate, drying the organic phases at the temperature of 30-35 ℃, carrying out pressure of 10-15 mmHg, carrying out reduced pressure concentration to obtain brown yellow crude products of 1.88kg, carrying out pressure quick distillation to obtain 768.6g of colorless transparent products, GC 76.5%.
3. And (3) rectification: distilling the colorless and transparent crude product with 30CM glass packed column by using a common water pump,
collecting front cut (external temperature 40-80 deg.C, top temperature 40-68 deg.C) 176g, GC 81.0%;
492g of the main fraction (external temperature 85-90 ℃, top temperature 68-72 ℃) was collected, GC: 98.36%, yield 43.2%.
Example 3
1. Adding 400g of magnesium chips and 2kg of tetrahydrofuran into a 10L reaction flask at 25 ℃ under the anhydrous and oxygen-free conditions of nitrogen protection to initiate reaction, supplementing 5kg of tetrahydrofuran (the system is gray black) after the initiation reaction is carried out for 0.5 hour, then introducing chloromethane gas, keeping the gas flow, continuously reacting until no magnesium chips exist, and keeping the temperature at room temperature for later use under the nitrogen protection, wherein the introduction amount of the chloromethane gas is 1662.5 g.
2. Adding 3, 3-dimethyl-2-butanone (550g) and 2.66kg (3L) tetrahydrofuran into a 20L reaction bottle, cooling to-18 ℃, slowly dropwise adding the Grignard reagent (dropwise adding while maintaining-18 ℃), keeping the temperature for 2 hours after dropwise adding, controlling the temperature of 1 raw material to be less than 5%, keeping the temperature for 12 ℃, dropwise adding methacrylic anhydride (2538.5g), keeping the temperature for 12 ℃ to react overnight (about 15 hours), pouring the post-treatment reaction liquid into 10L 1mol/L hydrochloric acid aqueous solution, stirring and layering, extracting the aqueous phase for 2 times by 3L ethyl acetate, washing the combined organic phase for 2 times by 3L/time of 5% sodium hydroxide aqueous solution, then washing for 1 time by 3L saturated salt, drying the organic phase by anhydrous sodium sulfate, concentrating under reduced pressure at 30-35 ℃ and 10-15 mmHg to obtain 1.62kg of brown yellow crude product, the product was rapidly distilled off under pressure to give 721g of a colorless transparent product having a GC content of 78%.
3. And (3) rectification: distilling the colorless and transparent crude product with a 30CM glass packed column by using a common water pump, and collecting 186g of front cut (the external temperature is 40-80 ℃, the top temperature is 40-68 ℃) and the GC is 85.6%; 460.6g of main fraction (external temperature 85-90 ℃, top temperature 68-72 ℃) were collected, the GC was 98.52%, and the yield was 45.5%.
The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.
Claims (9)
1. A preparation method of acid-sensitive photoresist resin monomer is characterized in that the reaction of the preparation method comprises the following synthetic route:
wherein R is1Is alkyl, R2Is a hydrogen atom or an alkyl group; the preparation method specifically comprises the following steps:
b) mixing the compound III with tetrahydrofuran, dripping a Grignard reagent at the temperature of-15 to-20 ℃, and carrying out heat preservation reaction;
c) and then, dropwise adding a compound II, carrying out heat preservation reaction at 10-15 ℃, and purifying to obtain the acid-sensitive photoresist resin monomer I.
2. The method of claim 1, further comprising at least one of the following features:
b1) in the step b), the molar ratio of the compound III to the Grignard reagent is 1: 1-1: 4;
b2) in the step b), the time of the heat preservation reaction is 1-5 hours.
3. The method of claim 1, further comprising at least one of the following features:
c1) in the step c), the molar ratio of the compound III to the compound II is 1: 1-1: 4;
c2) in the step c), the time of the heat preservation reaction is 12-24 hours.
4. The method for preparing acid sensitive photoresist resin monomer according to claim 1, wherein the purification in step c) comprises the steps of:
d) adding a hydrochloric acid aqueous solution into a reaction solution obtained after the heat preservation reaction in the step c), and stirring to obtain a first water phase and a first organic phase;
e) adding ethyl acetate into the first water phase for extraction to obtain a second water phase and a second organic phase; continuously adding ethyl acetate into the second water phase for extraction to obtain a third water phase and a third organic phase;
f) combining the first organic phase, the second organic phase and the third organic phase, and obtaining a crude product after alkali washing, salt washing, drying, reduced pressure concentration and distillation;
g) and rectifying the crude product.
5. The method of claim 4, further comprising at least one of the following features:
d1) in the step d), the concentration of the hydrochloric acid aqueous solution is 0.5-2 mol/L;
d2) the volume ratio of the addition amount of the hydrochloric acid aqueous solution to the reaction solution obtained after the heat preservation reaction is 1: (2-5).
6. The method of claim 4, further comprising at least one of the following features:
f1) in the step f), the alkali liquor used for alkali washing is NaOH solution with the mass concentration of 5 percent for washing; the number of the alkaline washing is at least 2;
f2) in step f), the salt washing is carried out by using a saturated NaCl solution;
f3) in step f), the drying agent used for drying is selected from anhydrous sodium sulfate or anhydrous magnesium sulfate;
f4) in the step f), the temperature for the reduced pressure concentration is 30-35 ℃, and the pressure is 10-15 mmHg; f5) in the step f), the distillation temperature is 40-50 ℃, and the distillation time is 4-6 hours.
7. The method for preparing the acid-sensitive photoresist resin monomer according to claim 4, further comprising the following technical features:
g1) in the step g), the rectification adopts segmented rectification, and fractions at the top of the tower with the external temperature of 85-90 ℃ and the top temperature of 68-72 ℃ are collected.
8. The method of preparing acid sensitive photoresist resin monomer of claim 1, wherein the method of preparation further comprises the preparation of a grignard reagent, the preparation of the grignard reagent comprising the steps of:
a) and (3) initiating a reaction between the magnesium chips and tetrahydrofuran in an inert environment, supplementing the tetrahydrofuran, and then introducing methyl halide until the magnesium chips are completely reacted to obtain the Grignard reagent.
9. The method of claim 8, further comprising at least one of the following features:
a1) the molar ratio of the magnesium chips to the methyl halide is 1: 2-1: 4;
a2) the methyl halide is selected from methyl chloride or methyl bromide;
a3) the temperature of the initiation reaction is 20-30 ℃, and the time of the initiation reaction is 0.5-1 hour;
a4) the inert environment is a nitrogen environment.
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