CN117865803A - Synthesis method of hydroquinone methacrylate photoresist monomer - Google Patents
Synthesis method of hydroquinone methacrylate photoresist monomer Download PDFInfo
- Publication number
- CN117865803A CN117865803A CN202410049900.9A CN202410049900A CN117865803A CN 117865803 A CN117865803 A CN 117865803A CN 202410049900 A CN202410049900 A CN 202410049900A CN 117865803 A CN117865803 A CN 117865803A
- Authority
- CN
- China
- Prior art keywords
- hydroquinone
- methacrylate
- photoresist monomer
- sodium bicarbonate
- synthesizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- SBRNNFKJRZCFRF-UHFFFAOYSA-N benzene-1,4-diol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.OC1=CC=C(O)C=C1 SBRNNFKJRZCFRF-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 title claims abstract description 14
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 14
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 11
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000012043 crude product Substances 0.000 claims abstract description 6
- 239000012065 filter cake Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000012074 organic phase Substances 0.000 claims abstract description 4
- 238000004537 pulping Methods 0.000 claims abstract description 4
- 239000011780 sodium chloride Substances 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- 239000012071 phase Substances 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 230000000886 photobiology Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 101100272976 Panax ginseng CYP716A53v2 gene Proteins 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a synthesis method of hydroquinone methacrylate photoresist monomer, which mainly solves the technical problems that the prior art method has low yield, is difficult to purify and cannot realize mass production. The synthesis method comprises (1) reacting hydroquinone, methacryloyl chloride, sodium bicarbonate in dichloromethane and water to obtain a reaction solution; (2) Separating phases of the obtained reaction liquid, and washing an organic phase with sodium bicarbonate, a hydrochloric acid aqueous solution and a sodium chloride aqueous solution in sequence to obtain a crude product solution; (3) Concentrating the crude product solution until solid is separated out, and stopping concentrating; (4) adding an organic solvent into the mixture for pulping; (5) Filtering, and drying the filter cake to obtain a target product, wherein the purity of the target product is more than 99%. The invention synthesizes the hydroquinone methacrylate by adopting a heterogeneous reaction mode for the first time, has simple and convenient operation and low cost, and is suitable for large-scale production.
Description
Technical Field
The invention relates to a synthesis method of hydroquinone methacrylate photoresist monomer.
Background
Hydroquinone methacrylate, the structure of which is shown in the following formula, is an important photoresist monomer, is widely applied to the field of semiconductors,
。
the direct reaction of hydroquinone and methacryloyl chloride under the action of a base generally results in a product in which two hydroxyl groups are esterified simultaneously. Journal of literature photochemistry and photobiology (Journal of Photochemistry and Photobiology A: chemistry, 2011, 219, 50-57) reports the reaction of methacryloyl chloride with hydroquinone, with triethylamine as base, in yields of only 35%, purification of the product requiring column chromatography, which is not amenable to large scale production. Patent KR101580028, 2015, B1, JP2022/14694, 2022, A and patent EP1970367, 2008, A2 report that methacrylic acid and hydroquinone are used for synthesizing hydroquinone methacrylate respectively, the method needs p-toluenesulfonic acid or PPTS, the reaction needs high temperature of 120 ℃ to be completed, the reaction condition is harsh, and the purification operation difficulty is relatively high. Patent JP5978938, 2016, B2 and patent JP2020/93995, 2020, A report that hydroquinone is subjected to single protection and then reacted with methacrylic acid or methacryloyl chloride, and finally subjected to deprotection to obtain a target product, and the method is complex in operation, high in cost and unfavorable for large-scale production.
Disclosure of Invention
The invention aims to provide a method for preparing hydroquinone methacrylate photoresist monomer, which has the advantages of simple operation, easy purification and easy industrial production. Mainly solves the technical problems that the prior art method is difficult to purify, has complex operation and high cost and cannot realize mass production.
The technical scheme of the invention is as follows:
a synthesis method of hydroquinone methacrylate photoresist monomer comprises the following steps:
(1) Hydroquinone, methacryloyl chloride and sodium bicarbonate react in dichloromethane and water to obtain a reaction solution;
(2) Separating phases of the obtained reaction liquid, and washing an organic phase with 10% sodium bicarbonate and 10% hydrochloric acid aqueous solution and 10% sodium chloride aqueous solution to obtain a crude product solution;
(3) Concentrating the crude product solution until solid is separated out, and stopping concentrating;
(4) Adding an organic solvent into the mixture for pulping;
(5) Filtering, and drying the filter cake to obtain the target product.
The reaction formula is as follows:
。
the molar ratio of the methacryloyl chloride to the hydroquinone used in the step (1) is 2:1, the molar ratio of the sodium bicarbonate to the hydroquinone is 2:1, the volume ratio of the methylene dichloride to the hydroquinone is 10:1, and the volume ratio of the water to the hydroquinone is 5:1.
The organic solvent in the step (4) is one or more selected from petroleum ether, n-hexane, n-pentane or cyclohexane.
Preferably, the organic solvent in the step (4) is petroleum ether, and the volume ratio of petroleum ether to hydroquinone is 5:1.
The drying temperature in the step (5) is 50 ℃ and the drying time is 12 hours.
The invention has the beneficial effects that: the invention adopts a heterogeneous reaction mode to synthesize the hydroquinone methacrylate photoresist monomer for the first time, the purity of the product can reach more than 99 percent, the operation is simple and convenient, the cost is low, and the mass production is easy to carry out.
Drawings
FIG. 1 is an HPLC chromatogram of a product of the present invention.
FIG. 2 is a nuclear magnetic resonance spectrum of the product of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific embodiments, to which the invention is not limited.
Examples
Hydroquinone (2 kg,18.2 mol), sodium bicarbonate (3.1 kg, 36.3 mol), methylene chloride (20L), methacryloyl chloride (3.8 kg, 36.3 mol) and water (10L) were added to a 50L reactor in sequence, and after the addition, the mixture was kept at room temperature and allowed to react overnight. Separating liquid, namely sequentially washing an organic phase by using 10% sodium bicarbonate with the mass percentage concentration, 10% hydrochloric acid water solution with the mass percentage concentration and 10% sodium chloride water solution with the mass percentage concentration, concentrating until solid is separated out, adding petroleum ether (10L), pulping, filtering, and drying a filter cake at 50 ℃ for 12 hours to obtain a target product of 1.8 kg, wherein the yield is: 56%, nuclear magnetism and purity are shown in fig. 2 and 1.
Claims (6)
1. A method for synthesizing hydroquinone methacrylate photoresist monomer is characterized in that: the method comprises the following steps:
(1) Hydroquinone, methacryloyl chloride and sodium bicarbonate react in dichloromethane and water to obtain a reaction solution;
(2) Separating phases of the obtained reaction liquid, and washing an organic phase with 10% sodium bicarbonate and 10% hydrochloric acid aqueous solution and 10% sodium chloride aqueous solution to obtain a crude product solution;
(3) Concentrating the crude product solution until solid is separated out, and stopping concentrating;
(4) Adding an organic solvent into the mixture for pulping;
(5) Filtering, and drying a filter cake to obtain a target product;
the reaction formula is as follows:
。
2. the method for synthesizing hydroquinone methacrylate photoresist monomer as claimed in claim 1, wherein the method comprises the following steps: the molar ratio of the methacryloyl chloride to the hydroquinone used in the step (1) is 2:1, the molar ratio of the sodium bicarbonate to the hydroquinone is 2:1, the volume ratio of the methylene dichloride to the hydroquinone is 10:1, and the volume ratio of the water to the hydroquinone is 5:1.
3. The method for synthesizing hydroquinone methacrylate photoresist monomer as claimed in claim 1, wherein the method comprises the following steps: the organic solvent in the step (4) is one or more selected from petroleum ether, n-hexane, n-pentane or cyclohexane.
4. A method for synthesizing hydroquinone methacrylate photoresist monomer according to claim 3, characterized in that: the organic solvent in the step (4) is petroleum ether.
5. A method for synthesizing hydroquinone methacrylate photoresist monomer according to claim 3, characterized in that: the volume ratio of the organic solvent to the hydroquinone in the step (4) is 5:1.
6. The method for synthesizing hydroquinone methacrylate photoresist monomer as claimed in claim 1, wherein the method comprises the following steps: the drying temperature in the step (5) is 50 ℃ and the drying time is 12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410049900.9A CN117865803A (en) | 2024-01-13 | 2024-01-13 | Synthesis method of hydroquinone methacrylate photoresist monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410049900.9A CN117865803A (en) | 2024-01-13 | 2024-01-13 | Synthesis method of hydroquinone methacrylate photoresist monomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117865803A true CN117865803A (en) | 2024-04-12 |
Family
ID=90586479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410049900.9A Pending CN117865803A (en) | 2024-01-13 | 2024-01-13 | Synthesis method of hydroquinone methacrylate photoresist monomer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117865803A (en) |
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2024
- 2024-01-13 CN CN202410049900.9A patent/CN117865803A/en active Pending
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