CN112794834A - Degradable resin monomer synthesized by 1, 6-dioxaspiro [2.5] octane and preparation method thereof - Google Patents
Degradable resin monomer synthesized by 1, 6-dioxaspiro [2.5] octane and preparation method thereof Download PDFInfo
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- CN112794834A CN112794834A CN202011548655.4A CN202011548655A CN112794834A CN 112794834 A CN112794834 A CN 112794834A CN 202011548655 A CN202011548655 A CN 202011548655A CN 112794834 A CN112794834 A CN 112794834A
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- resin monomer
- dioxaspiro
- octane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/10—Oxygen atoms
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention belongs to a degradable photoresist resin monomer, and discloses a composite material composed of 1, 6-dioxaspiro [2.5]]The degradable resin monomer synthesized by octane and the preparation method thereof are disclosed, wherein the structural formula of the resin monomer is as follows:
Description
Technical Field
The invention relates to the field of degradable photoresist resin monomers, in particular to a degradable resin monomer synthesized by 1, 6-dioxaspiro [2.5] octane and a preparation method thereof.
Background
The main components of the photoresist material are resin, photoacid generator, and corresponding additives and solvents, and the material has chemical sensitivity with light (including visible light, ultraviolet light, electron beam, etc.) and changes its solubility in developer through photochemical reaction.
The resin used in the photoresist is a polymer formed by copolymerizing a plurality of resin monomers, wherein the acid-sensitive resin monomer is an important component for realizing the dissolution difference of the resin in a developing solution before and after exposure, the common acid-sensitive resin monomer only has one acid-sensitive group, the polymer resin is linear, the solubility difference between an exposed area and an unexposed area is formed by deprotection after the exposure of the acid-sensitive group, and the main chain of the linear polymer cannot be broken. Therefore, the existing photoresist has the problem of lower resolution of the photoetching pattern due to the specific structure of the acid-sensitive resin monomer.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a degradable resin monomer synthesized by 1, 6-dioxaspiro [2.5] octane and a preparation method thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention relates to a degradable resin monomer synthesized by 1, 6-dioxaspiro [2.5] octane, which has the following structural general formula:
As a preferred embodiment of the present invention, the resin monomer comprises the following structure:
As a preferred embodiment of the present invention, the resin monomer comprises the following structure:
a preparation method of a degradable resin monomer synthesized by 1, 6-dioxaspiro [2.5] octane comprises the following steps: the resin monomer is generated by ring-opening esterification of 1, 6-dioxaspiro [2.5] octane.
As a preferred technical scheme of the invention, the synthetic route is as follows:
the synthesis steps are as follows: and (2) heating and stirring the 1, 6-dioxaspiro [2.5] octane and methacrylic anhydride under the condition of 1, 8-diazabicyclo [5.4.0] undec-7-ene, and purifying to obtain a resin monomer.
As a preferred embodiment of the present invention,
the synthetic route is as follows:
wherein R is1Is alkanyl or cycloalkyl;
the method comprises the following steps: firstly, heating and stirring the 1, 6-dioxaspiro [2.5] octane and an acrylic compound II containing carboxyl under the condition of 1, 8-diazabicyclo [5.4.0] undec-7-ene, and purifying to obtain an intermediate compound III; and then, carrying out esterification reaction on the intermediate compound III and methacryloyl chloride to obtain a resin monomer IV.
As a preferable technical scheme of the invention, the acrylic compound II containing carboxyl is synthesized by the following steps: carrying out esterification reaction on a hydroxycarboxylic acid compound I and methacryloyl chloride under an alkaline condition, and purifying to obtain an acrylic acid compound II; wherein the hydroxycarboxylic acid compound I comprises the following structure:
compared with the prior art, the invention has the following beneficial effects:
(1) the resin monomer also contains a tert-butyl structure, during exposure, a photoacid generator group on the resin can generate sulfonic acid, and under the action of acid, the tert-butyl structure can be disconnected, so that a polymerization main chain is disconnected, small fragments are generated, the edge roughness of a photoetching pattern is improved, the resolution of the photoresist is improved, meanwhile, hydroxyl with good alkali dissolution is formed, the dissolution in the developing process is facilitated, the dissolution speed of the photoresist in a developing solution after exposure is increased, and the contrast of the photoresist is increased.
(2) The etching resistance of the photoresist is also greatly improved by the annular structure of the 1, 6-dioxaspiro [2.5] octane, and the solubility of the polyester-based structure of the resin monomer in a fat-soluble solvent is also improved by the polyester-based structure of the resin monomer, so that the spin coating is convenient and uniform.
(3) The invention has simple synthetic route and convenient operation.
Detailed Description
It should be understood that the preferred embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the present invention.
Example 1
Preparation of resin monomer Compound 1-2:
1, 6-dioxaspiro [2.5] octane 1-1(2g, 17.5mmol) was dissolved in dimethylformamide (20g) under nitrogen, and after dissolution, 1, 8-diazabicyclo [5.4.0] undec-7-ene (0.5g, 3.3mmol) and methacrylic anhydride (8.1g, 52.5mmol) were added, followed by stirring at 120 ℃ for 12 hours. The reaction mixture was extracted with ether to obtain an extract, which was washed with water and concentrated to give 1-2(2.4g, 8.9mmol, molar yield 51.0%) of the resin monomer.
Example 2
Preparation of Compound 2-2: glycolic acid 2-1(2g, 26.3mmol), triethylamine (2.7g, 26.7mmol) were dissolved in dichloromethane (20g), methacryloyl chloride (2.8g, 26.7mmol) was added dropwise to the mixture at 0 ℃ under nitrogen, stirring for 30 minutes, and stirring was continued at room temperature for 4 hours. Water was added, pH was adjusted, organic phase was extracted, and concentrated to give crude product, which was purified by column chromatography to give compound 2-2(3g, 20.8mmol, 79.1% molar yield).
Preparation of Compounds 2-3: 1, 6-dioxaspiro [2.5] octane (2g, 17.5mmol) was dissolved in dimethylformamide (20g) under nitrogen, and after the dissolution, 1, 8-diazabicyclo [5.4.0] undec-7-ene (0.5g, 3.3mmol) and compound 2-2(2.6g, 18.0mmol) were added and stirred at 120 ℃ for 5 hours. The reaction mixture was extracted with ether to obtain an extract, which was washed with water, concentrated, and the concentrate was added to hexane to conduct recrystallization, thereby obtaining solid compound 2-3(2.5g, 9.7mmol, molar yield 55.2%).
Preparation of resin monomer Compounds 2-4: compound 2-3(2.5g, 9.7mmol), triethylamine (1g, 9.9mmol) were dissolved in dichloromethane (40g), methacryloyl chloride (1.1g, 10.5mmol) was added dropwise to the mixture at 0 ℃ under nitrogen, stirring for 30 minutes, and stirring was continued at room temperature for 4 hours. Water was added, extraction was carried out to obtain an organic phase, concentration was carried out to obtain a crude product, and the crude product was purified by column chromatography to obtain resin monomer 2-4(2.6g, 8.0mmol, molar yield 82.3%).
Example 3
Preparation of Compound 3-2: 4-Hydroxycyclohexanecarboxylic acid 3-1(4g, 27.7mmol) and triethylamine (3g, 29.6mmol) were dissolved in dichloromethane (40g), and methacryloyl chloride (3g, 28.7mmol) was added dropwise to the above mixture at 0 ℃ under nitrogen, stirred for 30 minutes, and then stirred at room temperature for 4 hours. Water was added, pH was adjusted, organic phase was extracted, and concentrated to give crude product, which was purified by column chromatography to give compound 3-2(4.7g, 22.1mmol, mole yield 79.8%).
Preparation of Compounds 3-3: 1, 6-dioxaspiro [2.5] octane (2g, 17.5mmol) was dissolved in dimethylformamide (60g) under nitrogen, and after dissolution, 1, 8-diazabicyclo [5.4.0] undec-7-ene (0.5g, 3.3mmol) and compound 3-2(3.8g, 17.9mmol) were added and stirred at 120 ℃ for 5 hours. The reaction mixture was extracted with ether to obtain an extract, which was washed with water, concentrated, and the concentrate was added to hexane to conduct recrystallization, thereby obtaining solid compound 3-3(3g, 9.2mmol, molar yield 52.5%).
Preparation of resin monomer Compound 3-4: compound 3-3(3g, 9.2mmol), triethylamine (1g, 9.9mmol) were dissolved in dichloromethane (50g), methacryloyl chloride (1g, 9.6mmol) was added dropwise to the above mixture at 0 deg.C under nitrogen, stirring for 30 minutes, and stirring was continued at room temperature for 4 hours. Water was added, extraction was carried out to obtain an organic phase, concentration was carried out to obtain a crude product, and the crude product was purified by column chromatography to obtain resin monomer 3-4(2.8g, 7.1mmol, molar yield 71.0%).
Example 4
Preparation of Compound 4-2: 3-hydroxyadamantane-1-carboxylic acid 4-1(5g, 25.5mmol), triethylamine (2.6g, 25.7mmol) were dissolved in dichloromethane (50g), methacryloyl chloride (2.7g, 25.8mmol) was added dropwise to the mixture at 0 deg.C under nitrogen, stirring for 30 minutes, and stirring was continued at room temperature for 4 hours. Water was added, pH was adjusted, organic phase was extracted, and concentrated to give crude product, which was purified by column chromatography to give compound 4-2(5.6g, 21.2mmol, molar yield 83.2%).
Preparation of Compounds 4-3: 1, 6-dioxaspiro [2.5] octane (2g, 17.5mmol) was dissolved in dimethylformamide (30g) under nitrogen, and after the dissolution, 1, 8-diazabicyclo [5.4.0] undec-7-ene (0.5g, 3.3mmol) and compound 4-2(4.7g, 17.8mmol) were added and stirred at 120 ℃ for 5 hours. The reaction mixture was extracted with ether to obtain an extract, which was washed with water, concentrated, and the concentrate was added to hexane to conduct recrystallization, thereby obtaining 4-3(3.5g, 9.2mmol, molar yield 52.8%) as a solid compound.
Preparation of resin monomer Compound 4-4: compound 4-3(3.5g, 9.2mmol), triethylamine (1g, 9.9mmol) were dissolved in dichloromethane (30g), methacryloyl chloride (1g, 9.6mmol) was added dropwise to the mixture at 0 deg.C under nitrogen, stirring for 30 minutes, and stirring was continued at room temperature for 4 hours. Water was added, extraction was carried out to obtain an organic phase, concentration was carried out to obtain a crude product, and the crude product was purified by column chromatography to obtain resin monomer 4-4(3.3g, 7.4mmol, molar yield 79.9%).
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A degradable resin monomer synthesized by 1, 6-dioxaspiro [2.5] octane is characterized in that the structural general formula of the resin monomer is as follows:
2. The degradable resin monomer synthesized from 1, 6-dioxaspiro [2.5] octane as claimed in claim 1, wherein the resin monomer comprises the following structure:
3. The degradable resin monomer synthesized from 1, 6-dioxaspiro [2.5] octane as claimed in claim 2, wherein the resin monomer comprises the following structure:
4. a preparation method of a degradable resin monomer synthesized by 1, 6-dioxaspiro [2.5] octane is characterized by comprising the following steps: the resin monomer is generated by ring-opening esterification of 1, 6-dioxaspiro [2.5] octane.
5. The method for preparing the degradable resin monomer synthesized from 1, 6-dioxaspiro [2.5] octane according to claim 4, wherein the synthetic route is as follows:
the synthesis steps are as follows: and (2) heating and stirring the 1, 6-dioxaspiro [2.5] octane and methacrylic anhydride under the condition of 1, 8-diazabicyclo [5.4.0] undec-7-ene, and purifying to obtain a resin monomer.
6. The method for preparing the degradable resin monomer synthesized from 1, 6-dioxaspiro [2.5] octane according to claim 4, wherein the synthetic route is as follows:
wherein R is1Is alkanyl or cycloalkyl;
the method comprises the following steps: firstly, heating and stirring the 1, 6-dioxaspiro [2.5] octane and an acrylic compound II containing carboxyl under the condition of 1, 8-diazabicyclo [5.4.0] undec-7-ene, and purifying to obtain an intermediate compound III; and then, carrying out esterification reaction on the intermediate compound III and methacryloyl chloride, and purifying to obtain a resin monomer IV.
7. The method for preparing the degradable resin monomer synthesized from 1, 6-dioxaspiro [2.5] octane according to claim 6, wherein the carboxyl group-containing acrylic compound II is synthesized by the following steps: carrying out esterification reaction on a hydroxycarboxylic acid compound I and methacryloyl chloride under an alkaline condition, and purifying to obtain an acrylic acid compound II; wherein the hydroxycarboxylic acid compound I comprises the following structure:
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| CN202011548655.4A CN112794834A (en) | 2020-12-23 | 2020-12-23 | Degradable resin monomer synthesized by 1, 6-dioxaspiro [2.5] octane and preparation method thereof |
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| CN202011548655.4A CN112794834A (en) | 2020-12-23 | 2020-12-23 | Degradable resin monomer synthesized by 1, 6-dioxaspiro [2.5] octane and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113416177A (en) * | 2021-06-24 | 2021-09-21 | 徐州博康信息化学品有限公司 | Main chain degradable photoresist resin monomer and preparation method and application thereof |
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| CN101855254A (en) * | 2007-11-13 | 2010-10-06 | 出光兴产株式会社 | Adamantane derivative, process for producing the same, and curable composition comprising the adamantane derivative |
| CN111056947A (en) * | 2019-12-28 | 2020-04-24 | 上海博栋化学科技有限公司 | Photoresist resin monomer synthesized from α -cedrene and synthesis method thereof |
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2020
- 2020-12-23 CN CN202011548655.4A patent/CN112794834A/en active Pending
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| CN101855254A (en) * | 2007-11-13 | 2010-10-06 | 出光兴产株式会社 | Adamantane derivative, process for producing the same, and curable composition comprising the adamantane derivative |
| CN111056947A (en) * | 2019-12-28 | 2020-04-24 | 上海博栋化学科技有限公司 | Photoresist resin monomer synthesized from α -cedrene and synthesis method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113416177A (en) * | 2021-06-24 | 2021-09-21 | 徐州博康信息化学品有限公司 | Main chain degradable photoresist resin monomer and preparation method and application thereof |
| CN113416177B (en) * | 2021-06-24 | 2022-10-25 | 徐州博康信息化学品有限公司 | Main chain degradable photoresist resin monomer and preparation method and application thereof |
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