CN113880694A - Synthesis method of hydroxyl-substituted styrene compound and synthesis method of photoresist resin monomer - Google Patents
Synthesis method of hydroxyl-substituted styrene compound and synthesis method of photoresist resin monomer Download PDFInfo
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- CN113880694A CN113880694A CN202111204947.0A CN202111204947A CN113880694A CN 113880694 A CN113880694 A CN 113880694A CN 202111204947 A CN202111204947 A CN 202111204947A CN 113880694 A CN113880694 A CN 113880694A
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 24
- 239000011347 resin Substances 0.000 title claims abstract description 24
- 229920005989 resin Polymers 0.000 title claims abstract description 24
- 239000000178 monomer Substances 0.000 title claims abstract description 22
- -1 hydroxyl-substituted styrene compound Chemical class 0.000 title claims abstract description 15
- 238000001308 synthesis method Methods 0.000 title abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 17
- 238000010189 synthetic method Methods 0.000 claims abstract 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 69
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 238000010791 quenching Methods 0.000 claims description 26
- 230000000171 quenching effect Effects 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 22
- 229950000688 phenothiazine Drugs 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 17
- 238000004821 distillation Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 230000002194 synthesizing effect Effects 0.000 claims description 13
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 12
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 10
- 239000012346 acetyl chloride Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- 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 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000004537 pulping Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 125000004423 acyloxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000002274 desiccant Substances 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- QRPRIOOKPZSVFN-UHFFFAOYSA-M methyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 QRPRIOOKPZSVFN-UHFFFAOYSA-M 0.000 claims description 2
- JNMIXMFEVJHFNY-UHFFFAOYSA-M methyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 JNMIXMFEVJHFNY-UHFFFAOYSA-M 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 description 20
- 239000012043 crude product Substances 0.000 description 16
- 238000004128 high performance liquid chromatography Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 12
- 238000005070 sampling Methods 0.000 description 12
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 8
- OSQPUMRCKZAIOZ-UHFFFAOYSA-N carbon dioxide;ethanol Chemical compound CCO.O=C=O OSQPUMRCKZAIOZ-UHFFFAOYSA-N 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 6
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical class OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- FBTSUTGMWBDAAC-UHFFFAOYSA-N 3,4-Dihydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1O FBTSUTGMWBDAAC-UHFFFAOYSA-N 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- FVQGEBOWYJAQNE-UHFFFAOYSA-N (2,3-diacetyloxy-5-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC(C=C)=CC(OC(C)=O)=C1OC(C)=O FVQGEBOWYJAQNE-UHFFFAOYSA-N 0.000 description 1
- BGDWDFVUSUCDHI-UHFFFAOYSA-N (2-acetyloxy-4-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C=C)C=C1OC(C)=O BGDWDFVUSUCDHI-UHFFFAOYSA-N 0.000 description 1
- WRPYDXWBHXAKPT-UHFFFAOYSA-N (2-ethenylphenyl) acetate Chemical group CC(=O)OC1=CC=CC=C1C=C WRPYDXWBHXAKPT-UHFFFAOYSA-N 0.000 description 1
- JEKQGWWKEWSQCU-UHFFFAOYSA-N (3-acetyloxy-5-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC(OC(C)=O)=CC(C=C)=C1 JEKQGWWKEWSQCU-UHFFFAOYSA-N 0.000 description 1
- ZZMFDMIBZYLXQE-UHFFFAOYSA-N 5-ethenylbenzene-1,2,3-triol Chemical compound OC1=CC(C=C)=CC(O)=C1O ZZMFDMIBZYLXQE-UHFFFAOYSA-N 0.000 description 1
- LYECQNYXCRATFL-UHFFFAOYSA-N 5-ethenylbenzene-1,3-diol Chemical compound OC1=CC(O)=CC(C=C)=C1 LYECQNYXCRATFL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- 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
- C07C67/62—Use of additives, e.g. for stabilisation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a synthetic method of a hydroxyl-substituted styrene compound and a synthetic method of a photoresist resin monomer. The synthesis method of the hydroxyl-substituted styrene compound comprises the following steps: a) the compound of formula I-2 is obtained by reacting the compound of formula I-1 with Witting reagent. The synthetic method of the photoresist resin monomer comprises the following steps: a) obtaining a compound of formula I-2 by adopting the synthesis method of the hydroxyl-substituted styrene compound; b) reacting the compound shown in the formula I-2 with an acylating reagent to obtain the photoresist resin monomer shown in the formula I-3. The synthesis method of the hydroxyl-substituted styrene compound and the photoresist resin monomer has high yield and high purity.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a synthesis method of a hydroxyl-substituted styrene compound and a synthesis method of a photoresist resin monomer.
Background
The hydroxyl-substituted styrene compound is an important chemical and medical intermediate and has wide application in the fields of photoresist technology and the like. The positive chemically amplified resist usually adopts poly-p-hydroxystyrene derivatives as acid-sensitive resin, and p-hydroxystyrene-containing high-molecular photoresists have become a key technology for photoetching 0.11 micrometer line width chips. Photoresist resin monomers (acyloxy-substituted styrenic compounds, e.g., p-acetoxystyrene) are an important aromatic compound that can be used as monomers to prepare resins, elastomers, adhesives, coatings, automotive finishes, inks, or photoresists, etc. Photoresist resin monomers (acyloxy-substituted styrenic compounds, e.g., p-acetoxystyrene) are also useful in electronic materials, as additives in elastomer and resin formulations. However, the problems of low yield and low purity exist in the prior synthesis of hydroxyl-substituted styrene compounds and photoresist resin monomers.
Disclosure of Invention
In view of the above-described drawbacks of the prior art, an object of the present invention is to provide a method for synthesizing a hydroxyl-substituted styrene compound and a method for synthesizing a photoresist resin monomer, which have high yield and high purity.
To achieve the above and other related objects, the present invention provides a method for synthesizing a hydroxy-substituted styrenic compound, comprising the steps of:
a) reacting a compound shown in the formula I-1 with a Witting reagent to obtain a compound shown in the formula I-2, wherein the reaction route is as follows:
wherein the reaction isIn the presence of a first organic solvent and a base; r11、R12、R13、R14And R15Each is independent and is selected from one of hydrogen atom, alkyl and hydroxyl; r11、R12、R13、R14And R15At least one of which is a hydroxyl group.
The hydroxyl-substituted styrene compound can be 2-hydroxystyrene, p-hydroxystyrene, 3, 4-dihydroxystyrene, 3, 5-dihydroxystyrene or 3,4, 5-trihydroxystyrene.
Preferably, at least one of the following technical features is also included:
a1) the Witting reagent is selected from at least one of methyl triphenyl phosphonium bromide, methyl triphenyl phosphonium iodide and methyl triphenyl phosphonium chloride;
a2) the first organic solvent is at least one selected from tetrahydrofuran, dichloromethane, chloroform, toluene and N, N' -dimethylformamide;
a3) the alkali is selected from one of sodium hydride, calcium hydride, potassium tert-butoxide, sodium tert-butoxide and sodium ethoxide;
a4) the molar ratio of the compound shown in the formula I-1 to the Witting reagent is 1: 1-1: 5, such as 1: 1-1: 3 or 1: 3-1: 5;
a5) the mass ratio of the compound of the formula I-1 to the first organic solvent is 1: 5-1: 15, such as 1: 5-1: 8.9 or 1: 8.9-1: 15;
a6) the molar ratio of the compound of the formula I-1 to the base is 1: 1-1: 6, such as 1: 1-1: 3 or 1: 3-1: 6;
a7) the molar ratio of the Witting reagent to the alkali is 1: 0.8-1: 2, such as 1: 0.8-1: 1, 1: 1-1: 1.2 or 1: 1.2-1: 2;
a8) the reaction temperature is 20-25 ℃;
a9) the step a) specifically comprises the following steps: and mixing the first organic solvent and the Witting reagent, cooling for the first time, adding the alkali, cooling for the second time, and adding the compound shown in the formula I-1 for reaction.
More preferably, in the feature a9), at least one of the following technical features is further included:
a91) the temperature is reduced to minus 5 to minus 10 ℃ for the first time, such as minus 5 to minus 8 ℃ or minus 8 to minus 10 ℃;
a92) the temperature is reduced to-65 to-75 ℃ for the second time, such as-65 to-70 ℃ or-70 to-75 ℃.
Preferably, the synthesis method further comprises: sequentially carrying out quenching reaction, pH value adjustment, liquid separation and organic phase addition on the reaction product obtained in the step a), adding a first polymerization inhibitor, carrying out reduced pressure concentration, extraction, drying, filtering and washing.
More preferably, at least one of the following technical characteristics is also included:
11) carrying out third temperature reduction before carrying out quenching reaction; even more preferably, the third temperature reduction is to-5 to-10 ℃, such as-5 to-7 ℃ or-7 to-10 ℃;
12) the quenching reaction adopts a quenching agent selected from at least one of water, ammonium chloride solution, sodium chloride solution, hydrochloric acid and sulfuric acid;
13) adjusting the pH to 7-8, such as 7-7.5 or 7.5-8;
14) the first polymerization inhibitor is selected from at least one of phenothiazine, p-methoxyphenol, hydroquinone, p-benzoquinone and p-tert-butylcatechol;
15) the pressure of the reduced pressure distillation is 50-200 Pa, such as 50-100 Pa or 100-200 Pa;
16) the temperature of the reduced pressure distillation is 30-35 ℃, such as 30-32 ℃ or 32-35 ℃;
17) the extracting agent adopted by the extraction is at least one selected from ethyl acetate, dichloromethane, dichloroethane, trichloroethane, toluene, tetrahydrofuran and methyltetrahydrofuran;
18) the drying agent is at least one of anhydrous sodium sulfate and anhydrous magnesium sulfate;
19) the washing is carried out by using a detergent selected from at least one of ethyl acetate, dichloromethane, dichloroethane, trichloroethane, toluene, tetrahydrofuran and methyltetrahydrofuran.
The second aspect of the present invention provides a method for synthesizing a photoresist resin monomer, comprising the following steps:
a) obtaining a compound of formula I-2 by adopting the synthesis method of the hydroxyl-substituted styrene compound;
b) reacting a compound shown in a formula I-2 with an acylating reagent to obtain the photoresist resin monomer shown in a structural formula I-3, wherein the reaction route is as follows:
wherein the reaction is carried out in the presence of a second organic solvent and a basic catalyst; r21、R22、R23、R24And R25Each independently selected from one of hydrogen atom, alkyl, alkoxy and acyloxy; r21、R22、R23、R24And R25At least one of them is an acyloxy group.
The photoresist resin monomer can be 2-acetoxystyrene, p-acetoxystyrene, 3, 4-diacetoxystyrene, 3, 5-diacetoxystyrene, 3,4, 5-triacetoxystyrene and p-methacryloxy.
Preferably, step b) further comprises at least one of the following technical features:
b1) the acylating agent is at least one selected from acetyl chloride, acetic anhydride and acetic acid;
b2) the second organic solvent is at least one selected from tetrahydrofuran, dichloromethane, chloroform, toluene and N, N' -dimethylformamide;
b3) the basic catalyst is at least one of diethylamine, triethylamine, isopropylamine, monomethylamine, hexamethylenediamine and hexylamine;
b4) the molar ratio of the compound of formula I-2 to the acylating agent is 1: 1-1: 5, such as 1: 1-1: 2 or 1: 2-1: 5;
b5) the molar ratio of the compound of formula I-2 to the second solvent is 1: 5-1: 10, such as 1: 5-1: 6.3 or 1: 6.3-1: 10;
b6) the molar ratio of the compound of formula I-2 to the basic catalyst is 1: 1-1: 5, such as 1: 1-1: 2 or 1: 2-1: 5;
b7) the reaction temperature is 10-20 ℃, such as 10-15 ℃ or 15-20 ℃;
b8) the step b) comprises the following steps: mixing the alkaline catalyst and the second organic solvent, adding the acylating reagent, and controlling the internal temperature to be-5-0 ℃, such as-5-3 ℃ or-3-0 ℃.
Preferably, the synthesis method further comprises: sequentially carrying out quenching reaction on the reaction product obtained in the step b), adjusting the pH value, separating liquid, washing an organic phase by water, adding a second polymerization inhibitor, carrying out rotary evaporation, carrying out first extraction and dissolution of residues, pulping, filtering, carrying out reduced pressure concentration on the filtrate, carrying out second extraction and dissolution of residues, adding a third polymerization inhibitor, and carrying out oil pump reduced pressure distillation.
More preferably, at least one of the following technical characteristics is also included:
21) the quenching reaction adopts a quenching agent selected from at least one of water, ammonium chloride solution, sodium chloride solution, hydrochloric acid and sulfuric acid;
22) adjusting the pH to 7-8, such as 7-7.5 or 7.5-8;
23) the second polymerization inhibitor is selected from at least one of phenothiazine, p-methoxyphenol, hydroquinone, p-benzoquinone and p-tert-butylcatechol;
24) the rotary evaporation temperature is 25-30 ℃, such as 25-28 ℃ or 28-30 ℃.
More preferably, at least one of the following technical characteristics is also included:
25) the third polymerization inhibitor is selected from at least one of phenothiazine, p-methoxyphenol, hydroquinone, p-benzoquinone and p-tert-butylcatechol;
26) the third polymerization inhibitor comprises phenothiazine and p-methoxyphenol, and the mass ratio of the phenothiazine to the p-methoxyphenol is 1: 0.1-1: 0.5, such as 1: 0.1-1: 0.2, 1: 0.2-1: 0.35 or 1: 0.35-1: 0.5;
27) the pressure of the reduced pressure distillation is 70-80 Pa, such as 70-75 Pa or 75-80 Pa;
28) the temperature of reduced pressure distillation is 90-95 ℃, such as 90-94 ℃ or 94-95 ℃;
29) the top temperature of the reduced pressure distillation is 56-58 ℃, such as 56-57 ℃ or 57-58 ℃.
Compared with the prior art, the synthesis method of the hydroxyl-substituted styrene compound and the photoresist resin monomer has high yield and purity.
Drawings
FIG. 1 is a schematic representation of the HPLC purity of the reaction product obtained after the reaction of example 1 with the addition of 2-hydroxybenzaldehyde.
FIG. 2 is a schematic representation of the HPLC purity of the reaction product obtained after the addition of acetyl chloride in example 1.
FIG. 3 is a graph showing the GC purity of the residue after vacuum concentration and suction drying in example 1.
FIG. 4 is a schematic GC purity of the distillate of example 1.
FIG. 5 is an NMR spectrum of the product of example 1.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
In the present invention, the equipment, raw materials, etc. used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
4450g of tetrahydrofuran, N, were added to a 10L four-necked flask2And (3) replacing, starting mechanical stirring, adding 4400g of methyl triphenyl phosphonium bromide, cooling to-5-10 ℃, adding 1378g of potassium tert-butoxide in batches, stirring for 2h after adding, cooling to-65-75 ℃, dropwise adding 500g of 2-hydroxybenzaldehyde, stirring overnight after dropwise adding and stirring for 2h, raising the temperature to room temperature (20-25 ℃), and sampling and analyzing, wherein the HPLC purity schematic diagram is shown in figure 1 (raw materials are less than 0.1%), and the HPLC purity is 82%.
Cooling the reaction liquid to-5-10 ℃, adding 1000g of water for quenching, adding 1800g of 10% HCl for adjusting the pH value to 7-8 after quenching, separating liquid, adding 2g of phenothiazine into an organic phase, concentrating under reduced pressure at 30-35 ℃, adding 2000g of dichloromethane for dissolving after concentrating, adding anhydrous magnesium sulfate, stirring until the solution is clear, filtering, leaching a filter cake with 200g of dichloromethane, and putting the filtrate into the next step, wherein the HPLC purity is 82%.
Adding 2516g of the filtrate in the previous step and 826.4g of triethylamine into a 10L four-mouth bottle, adding 2200g of dichloromethane, mechanically stirring, cooling by a dry ice-ethanol bath, beginning to dropwise add 641.4g of acetyl chloride, wherein the dropwise addition needs 1h, and controlling the internal temperature at-5-0 ℃; after the dropwise addition is finished, removing the dry ice-ethanol bath, continuing to react at 10-20 ℃ for 3h, sampling and analyzing, wherein the HPLC purity schematic diagram is shown in figure 2 (raw materials are less than 0.2%), and the purity is 87.9%.
After the reaction is finished, 1000g of water is added into the reaction liquid for quenching, 10% of sodium hydroxide aqueous solution is added for regulating the pH value to 7-8, liquid separation is carried out, 1000g of water is added into an organic phase for washing for 1 time, 2g of phenothiazine is added after the water washing is finished, water is heated at 25-30 ℃ for rotary evaporation, an oil pump is used for pumping out solvent residues to obtain a crude product, 800g multiplied by 4 times of n-hexane is added into the crude product for pulping at room temperature, filtration is carried out, reduced pressure concentration is carried out on filtrate, then the solvent residues are pumped out, sampling analysis is carried out, a GC purity schematic diagram is shown in figure 3 (the solvent residues are less than 0.5%), the crude product 800.5g with the purity of 73%, 1g of phenothiazine and 0.2g of p-methoxyphenol are added into the crude product, then the oil pump (70-80 Pa) is used for reduced pressure distillation, the oil bath temperature is 90-95 ℃, the top temperature is 56-58 ℃ to produce a fraction 508g, the sample analysis is shown in figure 4, the GC purity schematic diagram is 98.18%, the molar yield is 76%, and an NMR spectrum is shown in figure 5.
Example 2
Tetrahydrofuran, N was added to a 10L four-necked flask2And (2) replacement, starting mechanical stirring, adding methyl triphenyl phosphonium bromide, cooling to-5 ℃, adding potassium tert-butoxide in batches, stirring for 2h after adding, cooling to-70 ℃, dropwise adding 500g of 2-hydroxybenzaldehyde, heating to room temperature after dropwise adding and stirring for 2h, stirring overnight, sampling and analyzing, wherein the HPLC purity is 81%, wherein the molar ratio of the 2-hydroxybenzaldehyde to the methyl triphenyl phosphonium bromide is 1:1, the mass ratio of the tetrahydrofuran to the tetrahydrofuran is 1:15, and the molar ratio of the potassium tert-butoxide to the potassium tert-butoxide is 1:1.
cooling the reaction liquid to-7 ℃, adding 1000g of water for quenching, adding 10% HCl for adjusting the pH value to 7.5 after quenching, separating liquid, adding 2g of phenothiazine into the organic phase, concentrating under reduced pressure (200Pa) at 35 ℃, adding 2000g of dichloromethane for dissolving after concentrating, adding anhydrous magnesium sulfate for stirring until the solution is clear, filtering, leaching a filter cake with 200g of dichloromethane, and putting the filtrate into the next step, wherein the HPLC purity is 81%.
Adding 2514g of the filtrate in the previous step and triethylamine into a 10L four-mouth bottle, supplementing dichloromethane, mechanically stirring, cooling by a dry ice-ethanol bath, beginning to dropwise add acetyl chloride for 1h, and controlling the internal temperature at 0 ℃; after the dropwise addition is finished, removing the dry ice-ethanol bath, continuing to react at 15 ℃ for 3h, sampling and analyzing, wherein the HPLC purity is 86%, and the molar ratio of the 2-hydroxystyrene to acetyl chloride is 1: 5. the molar ratio to dichloromethane was 1: 10. the molar ratio of triethylamine to the compound is 1: 5.
after the reaction is finished, 1000g of water is added into the reaction liquid for quenching, 10% of sodium hydroxide aqueous solution is added for regulating the pH value to 8, liquid separation is carried out, 1000g of water is added into an organic phase for washing for 1 time, 2g of phenothiazine is added after the water washing is finished, the water is heated at 28 ℃ for rotary evaporation, an oil pump is used for pumping the solvent residue to obtain a crude product, 800g multiplied by 4 times of n-hexane is added into the crude product for pulping at room temperature, filtration is carried out, the filtrate is subjected to reduced pressure concentration, the solvent residue is pumped out again, sampling analysis is carried out to obtain 850g of the crude product, the GC purity is 69%, 1g of phenothiazine and 0.1g of p-methoxyphenol (the mass ratio is 1: 0.1) are added into the crude product, then the oil pump (80Pa) is used for reduced pressure distillation, the oil bath temperature is 95 ℃, the top temperature is 58 ℃, the oil bath purity is 97.1%, and the molar yield is 74.4%.
Example 3
Tetrahydrofuran, N was added to a 10L four-necked flask2And (2) replacement, starting mechanical stirring, adding methyl triphenyl phosphonium bromide, cooling to-8 ℃, adding potassium tert-butoxide in batches, stirring for 2h after adding, cooling to-65 ℃, dropwise adding 500g of 2-hydroxybenzaldehyde, heating to room temperature after dropwise adding and stirring for 2h, stirring overnight, sampling and analyzing, wherein the HPLC purity is 80%, wherein the molar ratio of the 2-hydroxybenzaldehyde to the methyl triphenyl phosphonium bromide is 1:5, the mass ratio of the tetrahydrofuran to the tetrahydrofuran is 1:5, and the molar ratio of the potassium tert-butoxide to the potassium tert-butoxide is 1: 6.
cooling the reaction liquid to-5 ℃, adding 1000g of water for quenching, adding 10% HCl for adjusting the pH value to 7 after quenching, separating liquid, adding 2g of phenothiazine into the organic phase, concentrating under reduced pressure (50Pa) at 30 ℃, adding 2000g of dichloromethane for dissolving after concentration, adding anhydrous magnesium sulfate for stirring until the solution is clear, filtering, leaching a filter cake by 200g of dichloromethane, and putting the filtrate into the next step, wherein the HPLC purity is 80%.
Adding 2519g of the filtrate in the previous step and triethylamine into a 10L four-mouth bottle, supplementing dichloromethane, mechanically stirring, cooling by a dry ice-ethanol bath, starting dropwise adding acetyl chloride for 1h, and controlling the internal temperature to be-5 ℃; after the dropwise addition, removing the dry ice-ethanol bath, continuing to react at 20 ℃ for 3h, sampling and analyzing, wherein the HPLC purity is 85%, and the molar ratio of the 2-hydroxystyrene to acetyl chloride is 1:1. the molar ratio to dichloromethane was 1: 5. the molar ratio of triethylamine to the compound is 1:1.
after the reaction is finished, 1000g of water is added into the reaction liquid for quenching, 10% of sodium hydroxide aqueous solution is added for regulating the pH value to 7.5, liquid separation is carried out, 1000g of water is added into an organic phase for washing for 1 time, 2g of phenothiazine is added after the water washing is finished and is subjected to rotary evaporation at the temperature of 30 ℃, an oil pump is used for pumping the residue to obtain a crude product, 800g multiplied by 4 times of n-hexane is added into the crude product for pulping at room temperature, filtration is carried out, the filtrate is subjected to reduced pressure concentration, the residue is pumped and dried, sampling analysis is carried out to obtain 750g of the crude product, the GC purity is 74%, 1g of phenothiazine and 0.5g of p-methoxyphenol (the mass ratio is 1: 0.5) are added into the crude product, then the oil pump (75Pa) is used for reduced pressure distillation, the oil bath temperature is 94 ℃, the top temperature is 57 ℃, the fraction 489g is obtained, the GC purity is 98%, and the molar yield is 73.2%.
Example 4
Tetrahydrofuran, N was added to a 10L four-necked flask2And (2) replacing, starting mechanical stirring, adding methyl triphenyl phosphonium bromide, cooling to-10 ℃, adding potassium tert-butoxide in batches, stirring for 2h after adding, cooling to-75 ℃, dropwise adding 500g of p-hydroxybenzaldehyde, heating to room temperature after dropwise stirring for 2h, stirring overnight, sampling and analyzing, wherein the HPLC purity is 81.5%, wherein the molar ratio of the p-hydroxybenzaldehyde to the methyl triphenyl phosphonium bromide is 1:3, the mass ratio of the p-hydroxybenzaldehyde to tetrahydrofuran is 1:6, and the molar ratio of the p-hydroxybenzaldehyde to the potassium tert-butoxide is 1: 6.
Cooling the reaction liquid to-10 ℃, adding 1000g of water for quenching, adding 10% HCl for adjusting the pH value to 8 after quenching, separating liquid, adding 2g of phenothiazine into an organic phase, concentrating under reduced pressure (100Pa) at 32 ℃, adding 2000g of dichloromethane for dissolving after concentration, adding anhydrous magnesium sulfate for stirring until the solution is clear, filtering, leaching a filter cake by 200g of dichloromethane, and putting the filtrate into the next step, wherein the HPLC purity is 79.9%.
Adding 2598g of the filtrate in the previous step and triethylamine into a 10L four-mouth bottle, supplementing dichloromethane, mechanically stirring, cooling by a dry ice-ethanol bath, beginning to dropwise add acetyl chloride for 1 hour, and controlling the internal temperature to be-3 ℃; after the dropwise addition, the dry ice-ethanol bath is removed, the reaction is continued at 10 ℃ for 3 hours, and then sampling analysis is carried out, wherein the HPLC purity is 81.3%, and the molar ratio of the p-hydroxystyrene to acetyl chloride is 1:3, the molar ratio of the p-hydroxystyrene to dichloromethane is 1:8, and the molar ratio of the p-hydroxystyrene to triethylamine is 1: 5.
After the reaction is finished, 1000g of water is added into the reaction liquid for quenching, 10% of sodium hydroxide aqueous solution is added for regulating the pH value to 7, liquid separation is carried out, 1000g of water is added into an organic phase for washing for 1 time, 2g of phenothiazine is added after the water washing is finished, the water is heated at 25 ℃ for rotary evaporation, an oil pump is used for pumping the solvent residue to obtain a crude product, 800g multiplied by 4 times of n-hexane is added into the crude product for pulping at room temperature, filtration is carried out, the filtrate is subjected to reduced pressure concentration, the solvent residue is pumped out again, sampling analysis is carried out to obtain 810g of the crude product, the GC purity is 69%, 1g of phenothiazine and 0.35g of p-methoxyphenol (the mass ratio is 1: 0.35) are added into the crude product, then the oil pump (70Pa) is used for reduced pressure distillation, the oil bath temperature is 90 ℃, the top temperature is 56 ℃, the oil bath is sampled and analyzed, the GC purity is 98.0%, and the molar yield is 73.8%.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A method for synthesizing a hydroxyl-substituted styrene compound is characterized by comprising the following steps:
a) reacting a compound shown in the formula I-1 with a Witting reagent to obtain a compound shown in the formula I-2, wherein the reaction route is as follows:
wherein the reaction is carried out in the presence of a first organic solvent and a base; r11、R12、R13、R14And R15Each is independent and is selected from one of hydrogen atom, alkyl and hydroxyl; r11、R12、R13、R14And R15At least one of which is a hydroxyl group.
2. The method of synthesizing a hydroxy-substituted styrenic compound of claim 1 further comprising at least one of the following technical features:
a1) the Witting reagent is selected from at least one of methyl triphenyl phosphonium bromide, methyl triphenyl phosphonium iodide and methyl triphenyl phosphonium chloride;
a2) the first organic solvent is at least one selected from tetrahydrofuran, dichloromethane, chloroform, toluene and N, N' -dimethylformamide;
a3) the alkali is selected from one of sodium hydride, calcium hydride, potassium tert-butoxide, sodium tert-butoxide and sodium ethoxide;
a4) the molar ratio of the compound shown in the formula I-1 to the Witting reagent is 1: 1-1: 5;
a5) the mass ratio of the compound of the formula I-1 to the first organic solvent is 1: 5-1: 15;
a6) the molar ratio of the compound of the formula I-1 to the base is 1: 1-1: 6;
a7) the molar ratio of the Witting reagent to the alkali is 1: 0.8-1: 2;
a8) the reaction temperature is 20-25 ℃;
a9) the step a) specifically comprises the following steps: and mixing the first organic solvent and the Witting reagent, cooling for the first time, adding the alkali, cooling for the second time, and adding the compound shown in the formula I-1 for reaction.
3. The method for synthesizing a hydroxyl-substituted styrene-based compound according to claim 2, wherein the characteristic a9) further comprises at least one of the following technical characteristics:
a91) the temperature is reduced to minus 5 to minus 10 ℃ for the first time;
a92) the temperature is reduced to-65 to-75 ℃ for the second time.
4. The method of synthesizing a hydroxy-substituted styrenic compound of claim 1, further comprising: sequentially carrying out quenching reaction, pH value adjustment, liquid separation and organic phase addition on the reaction product obtained in the step a), adding a first polymerization inhibitor, carrying out reduced pressure concentration, extraction, drying, filtering and washing.
5. The method of synthesizing a hydroxy-substituted styrenic compound of claim 4 further comprising at least one of the following technical features:
11) carrying out third temperature reduction before carrying out quenching reaction;
12) the quenching reaction adopts a quenching agent selected from at least one of water, ammonium chloride solution, sodium chloride solution, hydrochloric acid and sulfuric acid;
13) adjusting the pH value to 7-8;
14) the first polymerization inhibitor is selected from at least one of phenothiazine, p-methoxyphenol, hydroquinone, p-benzoquinone and p-tert-butylcatechol;
15) the pressure of the reduced pressure distillation is 50-200 Pa;
16) the temperature of reduced pressure distillation is 30-35 ℃;
17) the extracting agent adopted by the extraction is at least one selected from ethyl acetate, dichloromethane, dichloroethane, trichloroethane, toluene, tetrahydrofuran and methyltetrahydrofuran;
18) the drying agent is at least one of anhydrous sodium sulfate and anhydrous magnesium sulfate;
19) the washing is carried out by using a detergent selected from at least one of ethyl acetate, dichloromethane, dichloroethane, trichloroethane, toluene, tetrahydrofuran and methyltetrahydrofuran.
6. A synthetic method of a photoresist resin monomer is characterized by comprising the following steps:
a) obtaining a compound of formula I-2 using the method of synthesis of a hydroxy-substituted styrenic compound of any of claims 1 to 5;
b) reacting a compound shown in a formula I-2 with an acylating reagent to obtain the photoresist resin monomer shown in a structural formula I-3, wherein the reaction route is as follows:
wherein the reaction is carried out in the presence of a second organic solvent and a basic catalyst; r21、R22、R23、R24And R25Each independently selected from one of hydrogen atom, alkyl, alkoxy and acyloxy; r21、R22、R23、R24And R25At least one of them is an acyloxy group.
7. The method for synthesizing a photoresist resin monomer according to claim 6, wherein the step b) further comprises at least one of the following technical features:
b1) the acylating agent is at least one selected from acetyl chloride, acetic anhydride and acetic acid;
b2) the second organic solvent is at least one selected from tetrahydrofuran, dichloromethane, chloroform, toluene and N, N' -dimethylformamide;
b3) the basic catalyst is at least one of diethylamine, triethylamine, isopropylamine, monomethylamine, hexamethylenediamine and hexylamine;
b4) the molar ratio of the compound of the formula I-2 to the acylating reagent is 1: 1-1: 5;
b5) the molar ratio of the compound of the formula I-2 to the second solvent is 1: 5-1: 10;
b6) the molar ratio of the compound of the formula I-2 to the basic catalyst is 1: 1-1: 5;
b7) the reaction temperature is 10-20 ℃;
b8) the step b) comprises the following steps: mixing the alkaline catalyst and the second organic solvent, adding the acylating reagent, and controlling the internal temperature to be-5-0 ℃.
8. The method of synthesizing a photoresist resin monomer of claim 6, further comprising: sequentially carrying out quenching reaction on the reaction product obtained in the step b), adjusting the pH value, separating liquid, washing an organic phase by water, adding a second polymerization inhibitor, carrying out rotary evaporation, carrying out first extraction and dissolution of residues, pulping, filtering, carrying out reduced pressure concentration on the filtrate, carrying out second extraction and dissolution of residues, adding a third polymerization inhibitor, and carrying out oil pump reduced pressure distillation.
9. The method for synthesizing a photoresist resin monomer according to claim 8, further comprising at least one of the following technical features:
21) the quenching reaction adopts a quenching agent selected from at least one of water, ammonium chloride solution, sodium chloride solution, hydrochloric acid and sulfuric acid;
22) adjusting the pH value to 7-8;
23) the second polymerization inhibitor is selected from at least one of phenothiazine, p-methoxyphenol, hydroquinone, p-benzoquinone and p-tert-butylcatechol;
24) the rotary evaporation temperature is 25-30 ℃.
10. The method for synthesizing a photoresist resin monomer according to claim 8, further comprising at least one of the following technical features:
25) the third polymerization inhibitor is selected from at least one of phenothiazine, p-methoxyphenol, hydroquinone, p-benzoquinone and p-tert-butylcatechol;
26) the third polymerization inhibitor comprises phenothiazine and p-methoxyphenol, and the mass ratio of the phenothiazine to the p-methoxyphenol is 1: 0.1-1: 0.5;
27) the pressure of the reduced pressure distillation is 70-80 Pa;
28) the temperature of reduced pressure distillation is 90-95 ℃;
29) the top temperature of the reduced pressure distillation is 56-58 ℃.
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|---|---|---|---|---|
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5763560A (en) * | 1994-12-05 | 1998-06-09 | Honshu Chemical Industry Co., Ltd. | Method of producing styrene derivatives |
| CN102001918A (en) * | 2010-09-27 | 2011-04-06 | 常州大学 | Preparation method of p-hydroxystyrene and derivates thereof |
| CN108640819A (en) * | 2018-06-12 | 2018-10-12 | 上海博栋化学科技有限公司 | A kind of method of one pot process hydroxy styrenes class compound |
| CN108911982A (en) * | 2018-07-19 | 2018-11-30 | 徐州博康信息化学品有限公司 | A kind of environment protection method for the styrene compound that synthesis acyloxy replaces |
-
2021
- 2021-10-15 CN CN202111204947.0A patent/CN113880694B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5763560A (en) * | 1994-12-05 | 1998-06-09 | Honshu Chemical Industry Co., Ltd. | Method of producing styrene derivatives |
| CN102001918A (en) * | 2010-09-27 | 2011-04-06 | 常州大学 | Preparation method of p-hydroxystyrene and derivates thereof |
| CN108640819A (en) * | 2018-06-12 | 2018-10-12 | 上海博栋化学科技有限公司 | A kind of method of one pot process hydroxy styrenes class compound |
| CN108911982A (en) * | 2018-07-19 | 2018-11-30 | 徐州博康信息化学品有限公司 | A kind of environment protection method for the styrene compound that synthesis acyloxy replaces |
Non-Patent Citations (6)
| Title |
|---|
| GUODONG LIU: "Stereoselective Synthesis of Benzannulated Spiroketals: Influence of the Aromatic Ring on Reactivity and Conformation", ORG. LETT., vol. 11, no. 16, pages 3670 - 3673 * |
| JUNG HA SHIN: "Electronically Mismatched Cycloaddition Reactions via First-Row Transition Metal, Iron(III)-Polypyridyl Complex", ORG. LETT., vol. 20, pages 5872 * |
| MINGJUN ZHANG: "The photoredox-catalyzed hydrosulfamoylation of styrenes and its application in the novel synthesis of naratriptan", CHEM. COMMUN., vol. 57, pages 9140 - 195 * |
| YUXIANG ZHU: "HFIP Solvent Enables Alcohols To Act as Alkylating Agents in Stereoselective Heterocyclization", J. AM. CHEM. SOC., vol. 141, pages 6489 * |
| 盛军波主编: "苯加氢操作技术", 31 January 2014, 北京：冶金工业出版社, pages: 78 - 81 * |
| 魏顺安，谭陆西主编: "化工工艺学", 31 May 2021, 重庆：重庆大学出版社, pages: 233 - 237 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116178145A (en) * | 2022-12-26 | 2023-05-30 | 徐州博康信息化学品有限公司 | Preparation method of fluorine-containing photoresist resin monomer and intermediate thereof |
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