CN114085138B - Preparation method of photoresist resin monomer and intermediate thereof - Google Patents
Preparation method of photoresist resin monomer and intermediate thereof Download PDFInfo
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- CN114085138B CN114085138B CN202111355875.XA CN202111355875A CN114085138B CN 114085138 B CN114085138 B CN 114085138B CN 202111355875 A CN202111355875 A CN 202111355875A CN 114085138 B CN114085138 B CN 114085138B
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 39
- 239000011347 resin Substances 0.000 title claims abstract description 27
- 229920005989 resin Polymers 0.000 title claims abstract description 27
- 239000000178 monomer Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 19
- 238000005886 esterification reaction Methods 0.000 claims abstract description 7
- 238000007273 lactonization reaction Methods 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 98
- 150000001875 compounds Chemical class 0.000 claims description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 77
- 239000012044 organic layer Substances 0.000 claims description 70
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 239000010410 layer Substances 0.000 claims description 56
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 22
- 238000000605 extraction Methods 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000012071 phase Substances 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 11
- 235000019253 formic acid Nutrition 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 8
- 238000004537 pulping Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 5
- 229950000688 phenothiazine Drugs 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000010009 beating Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 64
- 238000004817 gas chromatography Methods 0.000 description 47
- 238000003756 stirring Methods 0.000 description 46
- 238000005070 sampling Methods 0.000 description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 239000000463 material Substances 0.000 description 29
- 238000005086 pumping Methods 0.000 description 27
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 230000001276 controlling effect Effects 0.000 description 15
- 239000007787 solid Substances 0.000 description 12
- -1 lactone compound Chemical class 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 230000003113 alkalizing effect Effects 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000007306 turnover Effects 0.000 description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/22—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by depolymerisation to the original monomer, e.g. dicyclopentadiene to cyclopentadiene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
Abstract
The invention provides a preparation method of a photoresist resin monomer and an intermediate thereof. The preparation method of the photoresist resin intermediate comprises the following steps: a)Depolymerizing to obtainb) Will beAnd (3) withThe reaction is carried out to obtainc) The reaction product of step b) is subjected to an alkalization treatment, an acidification treatment and a concentration. The preparation method of the photoresist resin monomer comprises the following steps: will beCarrying out an epoxidation reaction with an oxidant, and then carrying out a lactonization reaction; then is combined withAnd (3) carrying out esterification reaction to obtain the photoresist resin monomer. The preparation method of the photoresist resin monomer and the intermediate thereof has the advantages of high yield and high purity, and particularly has the advantages of high yield and high purity under hundred kg preparation.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of a photoresist resin monomer and an intermediate thereof.
Background
Photoresist (Photoresist), which is also called Photoresist, refers to a resist etching thin film material whose solubility is changed by irradiation or radiation of ultraviolet light, electron beam, ion beam, X-ray, or the like. A light-sensitive mixed liquid composed of 3 main components of photosensitive resin, sensitizer and solvent. Used as a corrosion resistant coating material during a photolithography process. When a semiconductor material is processed on a surface, a desired image can be obtained on the surface by using a photoresist with proper selectivity. Photoresists are classified into two major classes, positive and negative, according to the images they form. In the photoresist process, after the coating is exposed and developed, the exposed part is dissolved, the unexposed part is left, and the coating material is positive photoresist. If the exposed portions remain and the unexposed portions are dissolved, the coating material is a negative photoresist. According to the different exposure light source and radiation source, ultraviolet photoresist (including ultraviolet positive and negative photoresist), deep ultraviolet photoresist, X-ray photoresist, electron beam photoresist, ion beam photoresist, etc. The lactone compound-containing resin monomer for photoresist can give resin sufficient and average etching resistance and substrate adhesion, and is widely applied to resin monomers for photoresist, but the existing preparation method has low yield and low purity.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a method for preparing a photoresist resin monomer and an intermediate thereof, which is high in yield and purity.
To achieve the above and other related objects, a first aspect of the present invention provides a method for preparing a photoresist resin intermediate, comprising the steps of:
a) Depolymerizing the compound of formula I-1 to obtain a compound of formula I-2, wherein the reaction route is as follows:
b) Reacting a compound of formula I-2 with a compound of formula I-3 to obtain a compound of formula I-4, wherein the reaction scheme is as follows:
c) Alkalizing, acidifying and concentrating the reaction product of the step b);
wherein R is 1 Is one of a hydrogen atom, a linear alkyl group, a branched alkyl group, and a cyclic alkyl group; r is R 2 Is hydrogen atom or CO 2 R 3 ；R 3 Is one of a hydrogen atom, a linear alkyl group, a branched alkyl group and a cyclic alkyl group.
R 1 Straight chain alkyl, branched alkyl or cyclic alkyl having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, sec-butyl, isobutyl, n-pentyl, t-pentyl, n-hexyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl and the like. R is R 3 Straight chain alkyl, branched alkyl or cyclic alkyl having 1 to 15 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, sec-butyl, isobutyl, n-pentyl, t-pentyl, n-hexyl, cyclopentyl, cyclohexyl, ethylcyclopentyl, butylcyclopentyl, ethylcyclohexyl, butylcyclohexyl, adamantyl, ethyladamantanyl, butyladamantanyl, and the like.
Preferably, the method further comprises at least one of the following technical characteristics:
a1 In step a), the depolymerization temperature is 150 to 200 ℃, such as 150 to 165 ℃ or 165 to 200 ℃;
a2 In step a), the depolymerization pressure is normal pressure; atmospheric pressure refers to one atmosphere;
a3 In step a), depolymerizing the collected fraction to a fraction at 36-42 ℃;
b1 In step b), the molar ratio of the compound of formula I-2 to the compound of formula I-3 is from 1 to 1.5:1, such as 1 to 1.09: 1. 1.09-1.2: 1 or 1.2 to 1.5:1, a step of;
b2 In step b), the reaction temperature is 38-42 ℃;
b2 Step b) is carried out under an inert gas such as nitrogen or the like;
c1 Step c) comprises the following steps:
c11 Mixing the reaction product of step b), a first organic solvent, a base and water, and layering to obtain an aqueous layer phase;
c12 Mixing the aqueous layer phase with acid, adding a second organic solvent, and layering to obtain an organic layer phase;
c13 Concentrating the organic layer phase to recover the first organic solvent and the second organic solvent.
More preferably, in the feature c 1), at least one of the following technical features is further included:
c111 In step c 11), the mass ratio of the reaction product of step b) to the first organic solvent is 2 to 5:1, such as 2 to 3.3: 1. 3.3 to 4:1 or 4 to 5:1, a step of;
c112 In step c 11), the pH value after mixing is 12-13;
c113 In step c 11), the first organic solvent is at least one selected from methyl tertiary butyl ether, methylene chloride or chloroform;
c114 In step c 11), the base is selected from at least one of sodium hydroxide or potassium hydroxide;
c1 In step c), cooling the reaction product of step b) to 20-30 ℃ before alkalizing;
c121 In step c 12), the mass ratio of the aqueous phase to the second organic solvent is 1 to 3:1, such as 1-2: 1 or 2 to 3:1, a step of;
c122 In step c 12), the pH value after mixing is 2-3;
c123 Step c 12), wherein the acid is at least one selected from hydrochloric acid, acetic acid or phosphoric acid;
c131 In step c 13), the temperature of the organic layer is controlled to be 35-45 ℃;
c132 In step c 13), the pressure of the concentration is 20 to 50mmHg, such as 20 to 30mmHg, 30 to 40mmHg or 40 to 50mmHg.
The second aspect of the present invention provides a method for preparing a photoresist resin monomer, comprising the steps of:
1) The compound of the formula I-4 is obtained by adopting the preparation method of the photoresist resin intermediate;
2) Epoxidizing the compound of the formula I-4 with an oxidant to obtain a compound of the formula I-5, wherein the reaction route is as follows:
3) Carrying out a lactonization reaction on a compound of the formula I-5 to obtain a compound of the formula I-6, wherein the reaction route is as follows:
4) Esterifying the compound of the formula I-6 with the compound of the formula I-7 to obtain the compound of the formula I, wherein the reaction route is as follows:
wherein R is 4 Is hydrogen atom, methyl or CO 2 R 3 ；R 5 Is a hydrogen atom, a methyl group or a CH 2 CO 2 R 3 。
Preferably, in step 2), at least one of the following technical features is further included:
21 The molar ratio of the compound of formula I-4 to the oxidizing agent is 1:1.0 to 2.0, such as 1:1.0 to 1.35 or 1:1.35 to 2.0;
22 The temperature of the epoxidation reaction is 57-63 ℃;
23 The oxidant is at least one selected from hydrogen peroxide, m-chloroperoxybenzoic acid or peroxyacetic acid;
24 Performing an epoxidation reaction in the presence of formic acid;
25 Step 2) further comprises the steps of: quenching reaction, extraction and concentration are carried out on the reaction product of the step 2).
More preferably, at least one of the following technical features is further included:
241 24) the molar ratio of the compound of formula I-4 to formic acid is from 1:1 to 2, such as from 1:1 to 1:1.5 or from 1:1.5 to 1:2;
251 In feature 25), the quenching agent used in the quenching reaction is at least one selected from sodium sulfite, sodium bisulfite, or sodium dithionite, i.e., sodium dithionite;
252 In feature 25), the extractant employed in the extraction is at least one selected from ethyl acetate, dichloromethane, dichloroethane, trichloroethane, toluene, tetrahydrofuran, or methyltetrahydrofuran;
253 In the step 25), the temperature of the extracted organic layer is controlled between 37 and 43 ℃ during concentration;
254 In feature 25), the pressure of the concentration is from 20 to 50mmHg, such as from 20 to 35mmHg, from 35 to 45mmHg, or from 45 to 50mmHg.
Preferably, in step 3), at least one of the following technical features is further included:
31 The lactonization reaction is carried out in the presence of methanol and potassium carbonate;
32 The temperature of the lactonization reaction is 15-25 ℃;
33 Step 3) further comprises the steps of: the reaction product of step 3) is subjected to a first concentration, extraction, drying and a second concentration.
More preferably, at least one of the following technical features is further included:
311 In feature 31), the molar ratio of the compound of formula I-5 to methanol is 1:2 to 5, such as 1: 2-1: 3 or 1: 3-1: 5, a step of;
312 In feature 31), the molar ratio of the compound of formula I-5 to potassium carbonate is 1:0.2 to 1, such as 1:0.2 to 1:0.6 or 1:0.6 to 1:1, a step of;
331 In the feature 33), the temperature is controlled to be 35-45 ℃ in the first concentration;
332 In feature 33), the pressure of the first concentration is 20 to 50mmHg, such as 20 to 30mmHg, 30 to 40mmHg, or 40 to 50mmHg;
333 Feature 33), first concentrating to remove methanol;
334 In feature 33), ethyl acetate and water are added for extraction;
335 In the feature 33), the temperature is controlled between 38 and 42 ℃ in the second concentration;
336 In feature 33), the pressure of the second concentration is 20 to 50mmHg, such as 20 to 30mmHg, 30 to 40mmHg, or 40 to 50mmHg;
337 Feature 33), the second concentration removes ethyl acetate.
Preferably, in step 4), at least one of the following technical features is further included:
41 A molar ratio of the compound of formula I-6 to the compound of formula I-7 of 1:1 to 1.5, such as 1:1 to 1:1.2, 1:1.2 to 1:1.3 or 1:1.3 to 1:1.5;
42 The temperature of the esterification reaction is 3-7 ℃;
43 The esterification reaction is carried out in the presence of triethylamine and methylene chloride;
44 Step 4) is carried out under the protection of inert gas;
45 Adding polymerization inhibitor during esterification reaction;
46 Step 3) further comprises the steps of: extracting, concentrating and pulping the reaction product in the step 3).
More preferably, at least one of the following technical features is further included:
431 In feature 43), the molar ratio of the compound of formula I-6 to triethylamine is 1:1.5 to 2, such as 1:1.5 to 1:1.8 or 1:1.8 to 1:2;
432 In feature 43), the molar ratio of the compound of formula I-6 to dichloromethane is 1:5 to 10, such as 1:5 to 1:7 or 1: 7-1: 10;
451 In feature 45), the polymerization inhibitor is selected from at least one of phenothiazine, p-methoxyphenol, hydroquinone, p-benzoquinone, or p-tert-butylcatechol;
452 In feature 45), the molar ratio of the compound of formula I-6 to the polymerization inhibitor is 1:0.01 to 0.05, such as 1:0.01 to 1:0.03 or 1:0.03 to 1:0.05;
461 In feature 46), adding the reaction product of step 3) to a water-phase extraction, extracting the aqueous phase with dichloroethane, and combining the organic phases;
462 Feature 46), concentrating to remove dichloromethane;
463 Feature 46), methanol is added for beating.
Compared with the prior art, the preparation method of the photoresist resin intermediate comprises the steps of alkalizing and acidizing the reaction product in the step b), so that the compound of the formula I-1, such as cyclopentadiene dimer (odor, cause the polymerization, and cause the polymerization, can be removed, and the purity of the photoresist resin monomer can be improved to more than 99%. The preparation method of the photoresist resin monomer and the intermediate thereof has the advantages of high yield and high purity, and particularly has the advantages of high yield and high purity under hundred kg preparation.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of the product prepared in example 1.
FIG. 2 is a mass spectrum of the product prepared in example 1.
Detailed Description
The technical scheme of the invention is further specifically described by the following specific examples. It should be understood that the practice of the invention is not limited to the following examples, but is intended to be within the scope of the invention in any form and/or modification thereof.
In the present invention, the equipment, materials, etc. used are commercially available or are commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
400kg of dicyclopentadiene is poured into a reaction kettle, the normal pressure internal temperature is about 165 ℃, the fraction is 36-42 ℃, the receiving device is cooled by ice bath, and a first feed liquid containing 1, 3-cyclopentadiene is collected.
200kg of acrylic acid is pumped into a 500L kettle, and the temperature is raised to 40+/-2 ℃ in the kettle. And under the protection of nitrogen in the kettle, the first feed liquid is dripped. The addition was completed for about 14 hours. After the first material is dripped, the temperature in the kettle is controlled at 40+/-2 ℃, the reaction is carried out for 6 hours at the temperature, sampling is carried out after the temperature is kept, and the GC is measured, so that the purity of the product is required to be more than 90%. And after the reaction is finished, cooling the circulating water to 25+/-5 ℃ to obtain a second feed liquid. Alkalizing: the second feed liquid was transferred into a 1000L kettle, 180kg of methyl tert-butyl ether was introduced into the kettle, and the mixture was stirred for 10 minutes. 400kg of water is added into a 500L kettle in advance, 140kg of sodium hydroxide is slowly added under the condition of cooling of circulating water, and the mixture is stirred and dissolved and pumped into a 1000L overhead tank. And (3) dropwise adding a sodium hydroxide aqueous solution into the material liquid kettle at the temperature of 25+/-5 ℃, stirring for 10 minutes after about 300L dropwise adding, sampling to measure the pH value, wherein the required pH value is 12-13, stirring for 10 minutes after the pH value is adjusted, and re-measuring the pH value. At pH 12-13, stirring was started for 30 min, and the mixture was allowed to stand for 1 hr to separate the layers (the product was in the water layer). And (3) barreling the organic layer, and sending a water layer sample to measure GC, wherein the impurity peak is required to be less than 1% and is qualified. After the detection is qualified, the water layer is put into a 1000L kettle, the organic layer is put into a 500L kettle, and methyl tertiary butyl ether is recovered at normal pressure. And (3) acidizing: pumping 300kg of hydrochloric acid into a 1000L kettle high-level tank, controlling the temperature of feed liquid in the kettle to be 25+/-2 ℃, dripping the hydrochloric acid in the high-level tank, adjusting the pH to 2-3, dripping about 250kg, sampling and measuring the pH, and detecting once after each dripping 20kg of hydrochloric acid if the sample is unqualified, so as to be qualified. After the pH value of the feed liquid in the kettle is regulated, 400kg of methyl tertiary butyl ether (the product is positioned in the organic layer) is pumped into the kettle, stirred for 30 minutes, kept still for 30 minutes, layered, the lower water layer is put into another 1000L kettle, and the organic layer is remained in the kettle. The temperature of the organic layer is controlled to be 40+/-5 ℃, methyl tertiary butyl ether (recovered methyl tertiary butyl ether can be used for application) is concentrated under reduced pressure until no liquid flows out, then the organic layer is further concentrated for 3 hours, sampling and GC (gas chromatography) measurement are carried out, the solvent residue is required to be less than 2%, and the concentration pressure is 50mmHg. Concentrate to the final feed as an oil yielding 369kg of an oil.
122kg of formic acid is pumped into the 1000L kettle, 369kg of oily matter is pumped into the 1000L kettle, and 369kg of hydrogen peroxide is pumped into the high-level tank of the 1000L kettle. 369kg of hydrogen peroxide is added dropwise, and the dropwise addition is completed for about 8 hours. After the dripping is finished, controlling the temperature to be 60+/-3 ℃, preserving the heat for 1 hour, sampling and measuring the GC after the heat preservation is finished, and requiring the raw material to be less than 0.5 percent. 350kg of water is pumped into a 1000L kettle in advance, 110kg of sodium sulfite is added under stirring, and after stirring for 30 minutes, the temperature in the kettle is reduced by 5+/-3 ℃. And (3) transferring the qualified feed liquid into the kettle at the temperature of 5+/-5 ℃ for about 8 hours. And (3) controlling the temperature in the kettle to 15+/-3 ℃, dropwise adding hydrochloric acid to adjust the pH value to 2-3, and weighing the feed liquid after the pH value is adjusted. Extraction was performed multiple times with ethyl acetate, the layers were separated, the organic layers were combined, and the aqueous layer was discarded after it was determined to be empty. The temperature of the organic layer is controlled to 40+/-3 ℃, the organic layer is concentrated under reduced pressure until no liquid flows out, the concentration is continued for 2 hours, the concentration pressure is 35mmHg, the sample is sampled and measured for GC, and the solvent residue is required to be less than 2%. Cooling to normal temperature after concentration, and weighing the feed liquid in the kettle in a clean barrel. An oil was produced: 435kg.
480kg of methanol is pumped into a 1000L kettle, 200kg of oily matter is pumped into the kettle, 60kg of potassium carbonate is added, the temperature is controlled to be 20+/-5 ℃, the stirring is carried out for 3 hours, the GC is sampled and measured, the intermediate state is required to be less than 5% (the intermediate state position is the first peak behind the main peak), if the GC is failed, the GC is sampled once every 1 hour until the GC is failed (the reaction time is 3 hours, the intermediate state is 6.02 percent, and the reaction time is 4.69 percent). And the reaction is qualified, the temperature in the kettle is controlled at 40+/-5 ℃, the pressure is reduced, the concentration is carried out until no liquid flows out, and the concentration pressure is 40mmHg. After the concentration in the kettle is finished, ethyl acetate is used for extraction for a plurality of times, the layers are separated, the organic layers are combined, and the water layer is discharged after no material is determined. And adding 25kg of anhydrous sodium sulfate into the organic layer kettle, stirring for 2 hours at room temperature, sampling and measuring the water content, wherein the water content is required to be less than 0.5%. And the qualified filtration is carried out, and after the filter cake is leached by EA20kg, the filtration is carried out. The temperature of the organic layer is controlled to be 40+/-2 ℃, the organic layer is decompressed and concentrated until no liquid flows out, the concentration pressure is 40mmHg, and a large amount of white solid is precipitated in the kettle after the concentration is finished, so that the yield is 59.25%.
610kg of feed liquid, 270kg of methylene dichloride and 132kg of triethylamine are pumped into a 1000L kettle, after the material pumping is finished, nitrogen is replaced, and 1100g of p-tert-butyl catechol is put into the kettle under the protection of nitrogen. Under the protection of nitrogen, the temperature in the kettle is controlled to be 5+/-2 ℃, 97kg of methacryloyl chloride is added dropwise, and the dropwise addition is completed in about 8 hours. After the dripping is finished, the temperature is kept at 5+/-2 ℃ for 2 hours, sampling is carried out, and the GC is measured, wherein the raw material is required to be less than 0.5 percent. 400kg of water is added into a 1000L kettle in advance, the temperature is reduced to 2+/-2 ℃, the temperature in the kettle is controlled below 15 ℃, and the reaction solution is transferred into a hydrolysis kettle for about 3 hours. After the transfer, stirring at room temperature for 30 minutes, standing for 30 minutes, layering, separating the lower organic layer into a turnover barrel, and adding 200kg of dichloromethane into the water layer. Stirring at room temperature for 30 min, standing for 30 min, layering, discharging the water layer after no material is determined, combining organic layers, adding 300kg of water, stirring at room temperature for 30 min, standing for 30 min, layering, discharging the water layer after no material is determined. 50kg of anhydrous sodium sulfate is added into the organic layer, the mixture is stirred for 2 hours at room temperature, the mixture is sampled and tested for water content, the water content is required to be less than 0.5 percent, the mixture is filtered, and a filter cake is filtered by 30kg of dichloromethane, leached and filtered. The methylene chloride (below 30 ℃ C.) was removed under reduced pressure. Adding a small amount of dichloromethane, pulping for 30 minutes, centrifuging the solid to determine no mechanical impurities, sampling the solid, measuring nuclear magnetism (see figure 1), mass spectrum (see figure 2), GC and GPC, wherein the GC is required to be more than 99%, the GPC is required to be more than 99% (GC: 99.7%, GPC: 99.5%), the yield is 72.47%, and if the solid is not qualified, pulping for one hour by using redistilled methanol, cooling to 0-5 ℃, and centrifuging.
Example 2
400kg of dicyclopentadiene is poured into a reaction kettle, the normal pressure internal temperature is about 200 ℃, the fraction is 36-42 ℃, the receiving device is cooled by ice bath, and a first feed liquid containing 1, 3-cyclopentadiene is collected.
Acrylic acid is pumped into a 500L kettle, and the molar ratio of the 1, 3-cyclopentadiene to the acrylic acid is 1:1, heating to 40+/-2 ℃ in the kettle. And under the protection of nitrogen in the kettle, the first feed liquid is dripped. The addition was completed for about 14 hours. After the first material is dripped, the temperature in the kettle is controlled at 40+/-2 ℃, the reaction is carried out for 6 hours at the temperature, sampling is carried out after the temperature is kept, and the GC is measured, so that the purity of the product is required to be more than 90%. And after the reaction is finished, cooling the circulating water to 25+/-5 ℃ to obtain a second feed liquid. Alkalizing: transferring the second feed liquid into a 1000L kettle, pumping methyl tertiary butyl ether (the mass ratio of the second feed liquid to the methyl tertiary butyl ether is 5:1) into the kettle, and stirring for 10 minutes. 400kg of water is added into a 500L kettle in advance, 140kg of sodium hydroxide is slowly added under the condition of cooling of circulating water, and the mixture is stirred and dissolved and pumped into a 1000L overhead tank. And (3) dropwise adding a sodium hydroxide aqueous solution into the material liquid kettle at the temperature of 25+/-5 ℃, stirring for 10 minutes after about 300L dropwise adding, sampling to measure the pH value, wherein the required pH value is 12-13, stirring for 10 minutes after the pH value is adjusted, and re-measuring the pH value. At pH 12-13, stirring was started for 30 min, and the mixture was allowed to stand for 1 hr to separate the layers (the product was in the water layer). And (3) barreling the organic layer, and sending a water layer sample to measure GC, wherein the impurity peak is required to be less than 1% and is qualified. After the detection is qualified, the water layer is put into a 1000L kettle, the organic layer is put into a 500L kettle, and methyl tertiary butyl ether is recovered at normal pressure. And (3) acidizing: pumping 300kg of hydrochloric acid into a 1000L kettle high-level tank, controlling the temperature of feed liquid in the kettle to be 25+/-2 ℃, dripping the hydrochloric acid in the high-level tank, adjusting the pH to 2-3, dripping about 250kg, sampling and measuring the pH, and detecting once after each dripping 20kg of hydrochloric acid if the sample is unqualified, so as to be qualified. After the pH value of the feed liquid in the kettle is regulated, methyl tertiary butyl ether (the product is positioned in the organic layer) is pumped into the kettle, and the mass ratio of the aqueous layer phase to the methyl tertiary butyl ether is 3:1, stirring for 30 min, standing for 30 min, layering, putting the lower water layer into another 1000L kettle, and keeping the organic layer in the kettle. The temperature of the organic layer is controlled to be 40+/-5 ℃, methyl tertiary butyl ether (recovered methyl tertiary butyl ether can be used for application) is concentrated under reduced pressure until no liquid flows out, then the organic layer is further concentrated for 3 hours, sampling and GC (gas chromatography) measurement are carried out, the solvent residue is required to be less than 2%, and the concentration pressure is 40mmHg. Concentrate to the final feed as an oil yielding 325kg of oil.
Formic acid was pumped into the 1000L kettle and the oil was pumped in with a molar ratio of compound of formula I-4 to formic acid of 1:2, pumping hydrogen peroxide into a 1000L kettle high-level tank, wherein the mol ratio of the compound of the formula I-4 to the hydrogen peroxide is 1:2. and (5) dropwise adding hydrogen peroxide for about 8 hours. After the dripping is finished, controlling the temperature to be 60+/-3 ℃, preserving the heat for 1 hour, sampling and measuring the GC after the heat preservation is finished, and requiring the raw material to be less than 0.5 percent. 350kg of water is pumped into a 1000L kettle in advance, 110kg of sodium sulfite is added under stirring, and after stirring for 30 minutes, the temperature in the kettle is reduced by 5+/-3 ℃. And (3) transferring the qualified feed liquid into the kettle at the temperature of 5+/-5 ℃ for about 8 hours. And (3) controlling the temperature in the kettle to 15+/-3 ℃, dropwise adding hydrochloric acid to adjust the pH value to 2-3, and weighing the feed liquid after the pH value is adjusted. Extraction was performed multiple times with ethyl acetate, the layers were separated, the organic layers were combined, and the aqueous layer was discarded after it was determined to be empty. The organic layer was concentrated under reduced pressure at 40.+ -. 3 ℃ until no liquid flowed out, and then continued to be concentrated for 2 hours at a concentration pressure of 45mmHg, and the solvent residue was required to be less than 2% by GC sampling. Cooling to normal temperature after concentration, and weighing the feed liquid in the kettle in a clean barrel. An oil was produced: 425kg. Pumping methanol into a 1000L kettle, pumping oily matter, adding potassium carbonate, wherein the molar ratio of the compound of the formula I-5 to the methanol is 1:2, the molar ratio of the potassium carbonate to the potassium carbonate is 1:0.2, controlling the temperature to 20+/-5 ℃, stirring for 3 hours, sampling and measuring GC, wherein the intermediate state is required to be less than 5% (the intermediate state position is the first peak behind the main peak), and sampling is carried out once every 1 hour if the sample is failed until the sample is qualified (the reaction is carried out for 3 hours, the intermediate state is 6.02%, and the reaction is carried out for 4 hours, and the intermediate state is 4.69%). And the reaction is qualified, the temperature in the kettle is controlled at 40+/-5 ℃, the pressure is reduced, the concentration is carried out until no liquid flows out, and the concentration pressure is 20mmHg. After the concentration in the kettle is finished, ethyl acetate is used for extraction for a plurality of times, the layers are separated, the organic layers are combined, and the water layer is discharged after no material is determined. And adding 25kg of anhydrous sodium sulfate into the organic layer kettle, stirring for 2 hours at room temperature, sampling and measuring the water content, wherein the water content is required to be less than 0.5%. And the qualified filtration is carried out, and after the filter cake is leached by EA20kg, the filtration is carried out. The temperature of the organic layer is controlled to be 40+/-2 ℃, the organic layer is decompressed and concentrated until no liquid flows out, the concentration pressure is 20mmHg, and a large amount of white solid is precipitated in the kettle after the concentration is finished, and the yield is 58.1%.
Pumping feed liquid into a 1000L kettle, pumping dichloromethane into the kettle, pumping triethylamine into the kettle, wherein the molar ratio of the compound of the formula I-6 to the dichloromethane is 1:5, the molar ratio of the triethylamine is 1:2, after the pumping is finished, nitrogen is replaced, and a polymerization inhibitor phenothiazine is added under the protection of nitrogen, wherein the molar ratio of the compound of the formula I-6 to the polymerization inhibitor is 1:0.01. under the protection of nitrogen, dropwise adding methacryloyl chloride at the temperature of 5+/-2 ℃ in the kettle, wherein the molar ratio of the compound of the formula I-6 to the compound of the formula I-7 is 1:1.5, about 8 hours after the completion of the dropwise addition. After the dripping is finished, the temperature is kept at 5+/-2 ℃ for 2 hours, sampling is carried out, and the GC is measured, wherein the raw material is required to be less than 0.5 percent. 400kg of water is added into a 1000L kettle in advance, the temperature is reduced to 2+/-2 ℃, the temperature in the kettle is controlled below 15 ℃, and the reaction solution is transferred into a hydrolysis kettle for about 3 hours. After the transfer, stirring at room temperature for 30 minutes, standing for 30 minutes, layering, separating the lower organic layer into a turnover barrel, and adding 200kg of dichloromethane into the water layer. Stirring at room temperature for 30 min, standing for 30 min, layering, discharging the water layer after no material is determined, combining organic layers, adding 300kg of water, stirring at room temperature for 30 min, standing for 30 min, layering, discharging the water layer after no material is determined. 50kg of anhydrous sodium sulfate is added into the organic layer, the mixture is stirred for 2 hours at room temperature, the mixture is sampled and tested for water content, the water content is required to be less than 0.5 percent, the mixture is filtered, and a filter cake is filtered by 30kg of dichloromethane, leached and filtered. The methylene chloride (below 30 ℃ C.) was removed under reduced pressure. Adding a small amount of dichloromethane, pulping for 30 minutes, centrifuging to determine that the solid is free of mechanical impurities, GC and GPC, wherein the GC is required to be more than 99%, the GPC is required to be more than 99% (GC: 99.5%, GPC: 99.5%), the yield is 71.3%, if the solid is not qualified, pulping for one hour by using the distilled methanol, cooling to 0-5 ℃, and centrifuging.
Example 3
400kg of dicyclopentadiene is poured into a reaction kettle, the normal pressure internal temperature is about 150 ℃, the fraction is 36-42 ℃, the receiving device is cooled by ice bath, and a first feed liquid containing 1, 3-cyclopentadiene is collected.
Acrylic acid was drawn into a 500L kettle with a molar ratio of 1, 3-cyclopentadiene to acrylic acid of 1.5:1, heating to 40+/-2 ℃ in the kettle. And under the protection of nitrogen in the kettle, the first feed liquid is dripped. The addition was completed for about 14 hours. After the first material is dripped, the temperature in the kettle is controlled at 40+/-2 ℃, the reaction is carried out for 6 hours at the temperature, sampling is carried out after the temperature is kept, and the GC is measured, so that the purity of the product is required to be more than 90%. And after the reaction is finished, cooling the circulating water to 25+/-5 ℃ to obtain a second feed liquid. Alkalizing: transferring the second feed liquid into a 1000L kettle, pumping methyl tertiary butyl ether (the mass ratio of the second feed liquid to the methyl tertiary butyl ether is 2:1) into the kettle, and stirring for 10 minutes. 400kg of water is added into a 500L kettle in advance, 140kg of sodium hydroxide is slowly added under the condition of cooling of circulating water, and the mixture is stirred and dissolved and pumped into a 1000L overhead tank. And (3) dropwise adding a sodium hydroxide aqueous solution into the material liquid kettle at the temperature of 25+/-5 ℃, stirring for 10 minutes after about 300L dropwise adding, sampling to measure the pH value, wherein the required pH value is 12-13, stirring for 10 minutes after the pH value is adjusted, and re-measuring the pH value. At pH 12-13, stirring was started for 30 min, and the mixture was allowed to stand for 1 hr to separate the layers (the product was in the water layer). And (3) barreling the organic layer, and sending a water layer sample to measure GC, wherein the impurity peak is required to be less than 1% and is qualified. After the detection is qualified, the water layer is put into a 1000L kettle, the organic layer is put into a 500L kettle, and methyl tertiary butyl ether is recovered at normal pressure. And (3) acidizing: pumping 300kg of hydrochloric acid into a 1000L kettle high-level tank, controlling the temperature of feed liquid in the kettle to be 25+/-2 ℃, dripping the hydrochloric acid in the high-level tank, adjusting the pH to 2-3, dripping about 250kg, sampling and measuring the pH, and detecting once after each dripping 20kg of hydrochloric acid if the sample is unqualified, so as to be qualified. After the pH value of the feed liquid in the kettle is regulated, methyl tertiary butyl ether (the product is positioned in the organic layer) is pumped into the kettle, and the mass ratio of the aqueous layer phase to the methyl tertiary butyl ether is 1:1, stirring for 30 min, standing for 30 min, layering, putting the lower water layer into another 1000L kettle, and keeping the organic layer in the kettle. The temperature of the organic layer is controlled to be 40+/-5 ℃, methyl tertiary butyl ether (recovered methyl tertiary butyl ether can be used for application) is concentrated under reduced pressure until no liquid flows out, then the organic layer is further concentrated for 3 hours, sampling and GC (gas chromatography) measurement are carried out, the solvent residue is required to be less than 2%, and the concentration pressure is 50mmHg. Concentrate to the final feed as an oil yielding 315kg of oil.
Formic acid was pumped into the 1000L kettle and the oil was pumped in with a molar ratio of compound of formula I-4 to formic acid of 1:1, pumping hydrogen peroxide into a 1000L kettle high-level tank, wherein the mol ratio of the compound of the formula I-4 to the hydrogen peroxide is 1:1. and (5) dropwise adding hydrogen peroxide for about 8 hours. After the dripping is finished, controlling the temperature to be 60+/-3 ℃, preserving the heat for 1 hour, sampling and measuring the GC after the heat preservation is finished, and requiring the raw material to be less than 0.5 percent. 350kg of water is pumped into a 1000L kettle in advance, 110kg of sodium sulfite is added under stirring, and after stirring for 30 minutes, the temperature in the kettle is reduced by 5+/-3 ℃. And (3) transferring the qualified feed liquid into the kettle at the temperature of 5+/-5 ℃ for about 8 hours. And (3) controlling the temperature in the kettle to 15+/-3 ℃, dropwise adding hydrochloric acid to adjust the pH value to 2-3, and weighing the feed liquid after the pH value is adjusted. Extraction was performed multiple times with ethyl acetate, the layers were separated, the organic layers were combined, and the aqueous layer was discarded after it was determined to be empty. The organic layer was concentrated under reduced pressure at 40.+ -. 3 ℃ until no liquid flowed out, and then continued to be concentrated for 2 hours at a concentration pressure of 50mmHg, and the solvent residue was required to be less than 2% by GC sampling. Cooling to normal temperature after concentration, and weighing the feed liquid in the kettle in a clean barrel. An oil was produced: 421kg.
Pumping methanol into a 1000L kettle, pumping oily matter, adding potassium carbonate, wherein the molar ratio of the compound of the formula I-5 to the methanol is 1:5, the molar ratio of the potassium carbonate to the potassium carbonate is 1:1, controlling the temperature to 20+/-5 ℃, stirring for 3 hours, sampling and measuring GC, wherein the intermediate state is required to be less than 5% (the intermediate state position is the first peak behind the main peak), and sampling is carried out once every 1 hour if the sample is failed until the sample is qualified (the reaction is carried out for 3 hours, the intermediate state is 6.02%, and the reaction is carried out for 4 hours, and the intermediate state is 4.69%). And the reaction is qualified, the temperature in the kettle is controlled at 40+/-5 ℃, the pressure is reduced, the concentration is carried out until no liquid flows out, and the concentration pressure is 50mmHg. After the concentration in the kettle is finished, ethyl acetate is used for extraction for a plurality of times, the layers are separated, the organic layers are combined, and the water layer is discharged after no material is determined. And adding 25kg of anhydrous sodium sulfate into the organic layer kettle, stirring for 2 hours at room temperature, sampling and measuring the water content, wherein the water content is required to be less than 0.5%. And the qualified filtration is carried out, and after the filter cake is leached by EA20kg, the filtration is carried out. The temperature of the organic layer is controlled to be 40+/-2 ℃, the organic layer is decompressed and concentrated until no liquid flows out, the concentration pressure is 50mmHg, and a large amount of white solid is precipitated in the kettle after the concentration is finished, so that the yield is 57.1%.
Pumping feed liquid into a 1000L kettle, pumping dichloromethane into the kettle, pumping triethylamine into the kettle, wherein the molar ratio of the compound of the formula I-6 to the dichloromethane is 1:10, the molar ratio of the triethylamine is 1:1.5, after the material extraction is finished, nitrogen is replaced, and a polymerization inhibitor phenothiazine is added under the protection of nitrogen, wherein the molar ratio of the compound of the formula I-6 to the polymerization inhibitor is 1:0.05. under the protection of nitrogen, dropwise adding methacryloyl chloride at the temperature of 5+/-2 ℃ in the kettle, wherein the molar ratio of the compound of the formula I-6 to the compound of the formula I-7 is 1:1, about 8 hours after the completion of the dropwise addition. After the dripping is finished, the temperature is kept at 5+/-2 ℃ for 2 hours, sampling is carried out, and the GC is measured, wherein the raw material is required to be less than 0.5 percent. 400kg of water is added into a 1000L kettle in advance, the temperature is reduced to 2+/-2 ℃, the temperature in the kettle is controlled below 15 ℃, and the reaction solution is transferred into a hydrolysis kettle for about 3 hours. After the transfer, stirring at room temperature for 30 minutes, standing for 30 minutes, layering, separating the lower organic layer into a turnover barrel, and adding 200kg of dichloromethane into the water layer. Stirring at room temperature for 30 min, standing for 30 min, layering, discharging the water layer after no material is determined, combining organic layers, adding 300kg of water, stirring at room temperature for 30 min, standing for 30 min, layering, discharging the water layer after no material is determined. 50kg of anhydrous sodium sulfate is added into the organic layer, the mixture is stirred for 2 hours at room temperature, the mixture is sampled and tested for water content, the water content is required to be less than 0.5 percent, the mixture is filtered, and a filter cake is filtered by 30kg of dichloromethane, leached and filtered. The methylene chloride (below 30 ℃ C.) was removed under reduced pressure. Adding a small amount of dichloromethane, pulping for 30 minutes, centrifuging to determine that the solid is free of mechanical impurities, GC and GPC, wherein the GC is required to be more than 99%, the GPC is required to be more than 99% (GC: 99.56%, GPC: 99.6%), the yield is 70.6%, if the solid is not qualified, pulping for one hour by using the distilled methanol, cooling to 0-5 ℃, and centrifuging.
Example 4
400kg of the compound of the formula I-1 is poured into a reaction kettle, the normal pressure internal temperature is about 165 ℃, the fraction is 36-42 ℃, the receiving device is cooled by ice bath, and the first feed liquid containing the compound of the formula I-2 is collected.
Into a 500L kettle, a compound of formula I-3 was pumped in a molar ratio of 1.2:1, heating to 40+/-2 ℃ in the kettle. And under the protection of nitrogen in the kettle, the first feed liquid is dripped. The addition was completed for about 14 hours. After the first material is dripped, the temperature in the kettle is controlled at 40+/-2 ℃, the reaction is carried out for 6 hours at the temperature, sampling is carried out after the temperature is kept, and the GC is measured, so that the purity of the product is required to be more than 90%. And after the reaction is finished, cooling the circulating water to 25+/-5 ℃ to obtain a second feed liquid. Alkalizing: transferring the second feed liquid into a 1000L kettle, pumping methyl tertiary butyl ether (the mass ratio of the second feed liquid to the methyl tertiary butyl ether is 4:1) into the kettle, and stirring for 10 minutes. 400kg of water is added into a 500L kettle in advance, 140kg of sodium hydroxide is slowly added under the condition of cooling of circulating water, and the mixture is stirred and dissolved and pumped into a 1000L overhead tank. And (3) dropwise adding a sodium hydroxide aqueous solution into the material liquid kettle at the temperature of 25+/-5 ℃, stirring for 10 minutes after about 300L dropwise adding, sampling to measure the pH value, wherein the required pH value is 12-13, stirring for 10 minutes after the pH value is adjusted, and re-measuring the pH value. At pH 12-13, stirring was started for 30 min, and the mixture was allowed to stand for 1 hr to separate the layers (the product was in the water layer). And (3) barreling the organic layer, and sending a water layer sample to measure GC, wherein the impurity peak is required to be less than 1% and is qualified. After the detection is qualified, the water layer is put into a 1000L kettle, the organic layer is put into a 500L kettle, and methyl tertiary butyl ether is recovered at normal pressure. And (3) acidizing: pumping 300kg of hydrochloric acid into a 1000L kettle high-level tank, controlling the temperature of feed liquid in the kettle to be 25+/-2 ℃, dripping the hydrochloric acid in the high-level tank, adjusting the pH to 2-3, dripping about 250kg, sampling and measuring the pH, and detecting once after each dripping 20kg of hydrochloric acid if the sample is unqualified, so as to be qualified. After the pH value of the feed liquid in the kettle is regulated, methyl tertiary butyl ether (the product is positioned in the organic layer) is pumped into the kettle, and the mass ratio of the aqueous layer phase to the methyl tertiary butyl ether is 2:1, stirring for 30 min, standing for 30 min, layering, putting the lower water layer into another 1000L kettle, and keeping the organic layer in the kettle. The temperature of the organic layer is controlled to be 40+/-5 ℃, methyl tertiary butyl ether (recovered methyl tertiary butyl ether can be used for application) is concentrated under reduced pressure until no liquid flows out, then the organic layer is further concentrated for 3 hours, sampling and GC (gas chromatography) measurement are carried out, the solvent residue is required to be less than 2%, and the concentration pressure is 30mmHg. Concentrating to obtain oily substance, and collecting 330kg of oily substance of the compound of formula I-4.
Formic acid was pumped into a 1000L kettle and an oil of the compound of formula I-4 was pumped in, the molar ratio of the compound of formula I-4 to formic acid being 1:1.5, pumping peracetic acid into a 1000L kettle high tank, wherein the molar ratio of the compound of the formula I-4 to the peracetic acid is 1:2. and (5) dropwise adding hydrogen peroxide for about 8 hours. After the dripping is finished, controlling the temperature to be 60+/-3 ℃, preserving the heat for 1 hour, sampling and measuring the GC after the heat preservation is finished, and requiring the raw material to be less than 0.5 percent. 350kg of water is pumped into a 1000L kettle in advance, 110kg of sodium sulfite is added under stirring, and after stirring for 30 minutes, the temperature in the kettle is reduced by 5+/-3 ℃. And (3) transferring the qualified feed liquid into the kettle at the temperature of 5+/-5 ℃ for about 8 hours. And (3) controlling the temperature in the kettle to 15+/-3 ℃, dropwise adding hydrochloric acid to adjust the pH value to 2-3, and weighing the feed liquid after the pH value is adjusted. Extraction was performed multiple times with ethyl acetate, the layers were separated, the organic layers were combined, and the aqueous layer was discarded after it was determined to be empty. The temperature of the organic layer is controlled to 40+/-3 ℃, the organic layer is concentrated under reduced pressure until no liquid flows out, the concentration is continued for 2 hours, the concentration pressure is 20mmHg, the sample is sampled and measured for GC, and the solvent residue is required to be less than 2%. Cooling to normal temperature after concentration, and weighing the feed liquid in the kettle in a clean barrel. Yielding an oil of the compound of formula I-5: 490kg.
Pumping methanol into a 1000L kettle, pumping oily matter, adding potassium carbonate, wherein the molar ratio of the compound of the formula I-5 to the methanol is 1:3, the molar ratio of the potassium carbonate to the potassium carbonate is 1:0.6, controlling the temperature to 20+/-5 ℃, stirring for 3 hours, sampling and measuring GC, wherein the intermediate state is required to be less than 5% (the intermediate state position is the first peak behind the main peak), and sampling is carried out once every 1 hour if the sample is failed until the sample is qualified (the reaction is carried out for 3 hours, the intermediate state is 6.02%, and the reaction is carried out for 4 hours, and the intermediate state is 4.69%). And the reaction is qualified, the temperature in the kettle is controlled at 40+/-5 ℃, the pressure is reduced, the concentration is carried out until no liquid flows out, and the concentration pressure is 30mmHg. After the concentration in the kettle is finished, ethyl acetate is used for extraction for a plurality of times, the layers are separated, the organic layers are combined, and the water layer is discharged after no material is determined. And adding 25kg of anhydrous sodium sulfate into the organic layer kettle, stirring for 2 hours at room temperature, sampling and measuring the water content, wherein the water content is required to be less than 0.5%. And the qualified filtration is carried out, and after the filter cake is leached by EA20kg, the filtration is carried out. The temperature of the organic layer is controlled to be 40+/-2 ℃, the organic layer is decompressed and concentrated until no liquid flows out, the concentration pressure is 30mmHg, and a large amount of white solid is precipitated in the kettle after the concentration is finished, and the yield is 59.2%.
Pumping feed liquid into a 1000L kettle, pumping dichloromethane into the kettle, pumping triethylamine into the kettle, wherein the molar ratio of the compound of the formula I-6 to the dichloromethane is 1:7, the molar ratio of the triethylamine is 1:1.8, after the material extraction is finished, nitrogen is replaced, and a polymerization inhibitor phenothiazine is added under the protection of nitrogen, wherein the molar ratio of the compound of the formula I-6 to the polymerization inhibitor is 1:0.03. under the protection of nitrogen, dropwise adding the acryloyl chloride of the compound of the formula I-7 at the temperature of 5+/-2 ℃ in the kettle, wherein the mol ratio of the compound of the formula I-6 to the compound of the formula I-7 is 1:1.2, about 8 hours after the completion of the dropwise addition. After the dripping is finished, the temperature is kept at 5+/-2 ℃ for 2 hours, sampling is carried out, and the GC is measured, wherein the raw material is required to be less than 0.5 percent. 400kg of water is added into a 1000L kettle in advance, the temperature is reduced to 2+/-2 ℃, the temperature in the kettle is controlled below 15 ℃, and the reaction solution is transferred into a hydrolysis kettle for about 3 hours. After the transfer, stirring at room temperature for 30 minutes, standing for 30 minutes, layering, separating the lower organic layer into a turnover barrel, and adding 200kg of dichloromethane into the water layer. Stirring at room temperature for 30 min, standing for 30 min, layering, discharging the water layer after no material is determined, combining organic layers, adding 300kg of water, stirring at room temperature for 30 min, standing for 30 min, layering, discharging the water layer after no material is determined. 50kg of anhydrous sodium sulfate is added into the organic layer, the mixture is stirred for 2 hours at room temperature, the mixture is sampled and tested for water content, the water content is required to be less than 0.5 percent, the mixture is filtered, and a filter cake is filtered by 30kg of dichloromethane, leached and filtered. The methylene chloride (below 30 ℃ C.) was removed under reduced pressure. If a small amount of dichloromethane exists, methanol is added to pulp for 30 minutes, centrifugation is carried out, the centrifugal I compound solid is determined to have no mechanical impurities, GC and GPC, the GC is required to be more than 99%, the GPC is required to be more than 99% (GC: 99.4%, GPC: 99.5%), the yield is 70.8%, if the product is not qualified, the product is pulped for one hour by re-steaming methanol, the temperature is reduced to 0-5 ℃, and the product is centrifuged.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (7)
1. A preparation method of a photoresist resin intermediate is characterized by comprising the following steps:
a) Depolymerizing the compound of formula I-1 to obtain a compound of formula I-2, wherein the reaction route is as follows:
b) Reacting the reaction product of step a) with a compound of formula I-3 to obtain a compound of formula I-4, wherein the molar ratio of the compound of formula I-2 to the compound of formula I-3 is 1 to 1.5:1, the reaction route is as follows:
c11 Cooling the reaction product of the step b) to 20-30 ℃, mixing the reaction product of the step b), a first organic solvent, alkali and water, wherein the pH value after mixing is 12-13, and layering to obtain a water layer phase; the mass ratio of the reaction product of the step b) to the first organic solvent is 2-5: 1, the first organic solvent is selected from at least one of methyl tertiary butyl ether, methylene dichloride or chloroform, and the alkali is selected from at least one of sodium hydroxide or potassium hydroxide;
c12 Mixing the aqueous layer phase with acid, adding a second organic solvent into the mixture, and layering the mixture to obtain an organic layer phase, wherein the pH value of the mixed mixture is 2-3; the mass ratio of the aqueous layer phase to the second organic solvent is 1-3: 1, wherein the acid is at least one of hydrochloric acid, acetic acid or phosphoric acid, and the second organic solvent is at least one of methyl tertiary butyl ether, methylene dichloride or chloroform;
c13 Concentrating the organic layer phase to recover the first organic solvent and the second organic solvent; the temperature of the organic layer is controlled to be 35-45 ℃, and the concentration pressure is 20-50 mmHg;
wherein R is 1 Is a hydrogen atom, a linear alkyl group, a branched alkyl group or a ringOne of the alkyl groups; r is R 2 Is hydrogen atom or CO 2 R 3 ；
R 3 Is one of a hydrogen atom, a linear alkyl group, a branched alkyl group and a cyclic alkyl group.
2. The method of preparing a photoresist resin intermediate according to claim 1, further comprising at least one of the following technical features:
a1 In step a), the depolymerization temperature is 150-200 ℃;
a2 In step a), the depolymerization pressure is normal pressure;
a3 In step a), depolymerizing the collected fraction to a fraction at 36-42 ℃;
b2 In step b), the reaction temperature is 38-42 ℃;
b2 Step b) is carried out under inert gas.
3. A method for preparing a photoresist resin monomer, which is characterized by comprising the following steps:
1) Obtaining a compound of formula I-4 using a process for the preparation of a photoresist resin intermediate according to any one of claims 1 to 2;
2) In the presence of formic acid, the compound of the formula I-4 and an oxidant are subjected to epoxidation reaction to obtain a compound of the formula I-5, wherein the reaction route is as follows:
the mol ratio of the compound of the formula I-4 to formic acid is 1:1-2; the mol ratio of the compound of the formula I-4 to the oxidant is 1:1.0-2.0, and the oxidant is at least one of hydrogen peroxide, m-chloroperoxybenzoic acid or peroxyacetic acid;
quenching reaction, extraction and concentration are carried out on the reaction product obtained in the step 2), and when the reaction product is concentrated, the temperature of an organic layer obtained by extraction is controlled at 37-43 ℃, and the concentration pressure is 20-50 mmHg; the quenching agent adopted in the quenching reaction is at least one of sodium sulfite, sodium bisulphite or sodium dithionite, and the extracting agent adopted in the extraction is at least one of ethyl acetate, methylene dichloride, dichloroethane, trichloroethane, toluene, tetrahydrofuran or methyltetrahydrofuran;
3) Carrying out a lactonization reaction on a compound of the formula I-5 to obtain a compound of the formula I-6, wherein the reaction route is as follows:
4) Esterifying the compound of the formula I-6 with the compound of the formula I-7 to obtain the compound of the formula I, wherein the reaction route is as follows:
wherein R is 4 Is hydrogen atom, methyl or CO 2 R 3 ；R 5 Is a hydrogen atom, a methyl group or a CH 2 CO 2 R 3 。
4. The method for preparing a photoresist resin monomer according to claim 3, wherein in step 3), at least one of the following technical features is further included:
31 The lactonization reaction is carried out in the presence of methanol and potassium carbonate;
32 The temperature of the lactonization reaction is 15-25 ℃;
33 Step 3) further comprises the steps of: the reaction product of step 3) is subjected to a first concentration, extraction, drying and a second concentration.
5. The method for preparing a photoresist resin monomer according to claim 4, further comprising at least one of the following technical features:
311 In feature 31), the molar ratio of the compound of formula I-5 to methanol is 1:2 to 5;
312 In feature 31), the molar ratio of the compound of formula I-5 to potassium carbonate is 1:0.2 to 1;
331 In the feature 33), the temperature is controlled to be 35-45 ℃ in the first concentration;
332 In feature 33), the pressure of the first concentration is 20 to 50mmHg;
333 Feature 33), first concentrating to remove methanol;
334 In feature 33), ethyl acetate and water are added for extraction;
335 In the feature 33), the temperature is controlled between 38 and 42 ℃ in the second concentration;
336 In feature 33), the pressure of the second concentration is 20 to 50mmHg;
337 Feature 33), the second concentration removes ethyl acetate.
6. The method for preparing a photoresist resin monomer according to claim 3, wherein in the step 4), at least one of the following technical features is further included:
41 A molar ratio of the compound of formula I-6 to the compound of formula I-7 of 1:1 to 1.5;
42 The temperature of the esterification reaction is 3-7 ℃;
43 The esterification reaction is carried out in the presence of triethylamine and methylene chloride;
44 Step 4) is carried out under the protection of inert gas;
45 Adding polymerization inhibitor during esterification reaction;
46 Step 3) further comprises the steps of: extracting, concentrating and pulping the reaction product in the step 3).
7. The method for preparing a photoresist resin monomer according to claim 6, further comprising at least one of the following technical features:
431 In feature 43), the molar ratio of the compound of formula I-6 to triethylamine is 1:1.5 to 2;
432 In feature 43), the molar ratio of the compound of formula I-6 to dichloromethane is 1:5 to 10;
451 In feature 45), the polymerization inhibitor is selected from at least one of phenothiazine, p-methoxyphenol, hydroquinone, p-benzoquinone, or p-tert-butylcatechol;
452 In feature 45), the molar ratio of the compound of formula I-6 to the polymerization inhibitor is 1:0.01 to 0.05;
461 In feature 46), adding the reaction product of step 3) to a water-phase extraction, extracting the aqueous phase with dichloroethane, and combining the organic phases;
462 Feature 46), concentrating to remove dichloromethane;
463 Feature 46), methanol is added for beating.
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