CN114478500B - Coumarin two-photon initiator and synthesis method and application thereof - Google Patents

Coumarin two-photon initiator and synthesis method and application thereof Download PDF

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CN114478500B
CN114478500B CN202210035676.9A CN202210035676A CN114478500B CN 114478500 B CN114478500 B CN 114478500B CN 202210035676 A CN202210035676 A CN 202210035676A CN 114478500 B CN114478500 B CN 114478500B
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CN114478500A (en
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黄宁
唐金
施敏敏
陈红征
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Zhejiang University ZJU
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • 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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Abstract

The invention discloses a coumarin two-photon initiator, a synthesis method and application thereof, and is characterized in that the solubility of the two-photon initiator is improved and the two-photon absorption section is improved by changing functional groups and the sites where the functional groups are located, so that more excellent two-photon polymerization initiation efficiency is obtained. The synthesis steps of the novel two-photon initiator are as follows: step one, introducing corresponding groups into the positions 2 and 5 of thiophene; step two, introducing ester groups on the basis of the products of the step one; step three, performing a Kenaonvinguel condensation reaction on the product of the step two and a salicylaldehyde derivative to generate a corresponding novel two-photon initiator; the novel two-photon initiator provided by the invention has higher sensitivity, larger two-photon absorption section and lower polymerization threshold, and shows excellent two-photon polymerization activity and stability.

Description

Coumarin two-photon initiator and synthesis method and application thereof
Technical Field
The invention belongs to the technical field of micro-nano processing and manufacturing and photosensitive materials, and particularly relates to a coumarin two-photon initiator and a synthesis method and application thereof.
Background
Two-photon absorption refers to a nonlinear optical process in which a substance absorbs two photons simultaneously under the excitation of a strong laser, and transitions from a ground state to a high-level excited state. Unlike conventional ultraviolet single photon polymerization, two-photon polymerization generally adopts near infrared (600-1000 nm) laser, has longer wavelength, lower energy, lower linear absorption and Rayleigh scattering, lower photon energy, and only two-photon absorption occurs at the position with the maximum laser intensity near the focus, so that the two-photon process has good space selectivity, less damage to samples and better light stability of the compound in the wavelength range. In addition, the liquid resin has higher permeability to near infrared light, and the two-photon absorption intensity is in direct proportion to the flat hair of the incident laser intensity, so that only the focal point can initiate two-photon polymerization by controlling the laser intensity, and the two-photon polymerization has a 'point' polymerization characteristic. The laser direct writing technology based on two-photon polymerization has wide application prospect in the fields of two-photon dynamic treatment, high-density 3D optical information storage, micro-nano processing, three-dimensional stereo forming and the like.
The two-photon initiator is an important component and a research key point of two-photon polymerization, and has decisive effects on polymerization initiation efficiency, micro-nano processing speed and precision. Research and development of a high-efficiency two-photon polymerization initiator has important practical significance and decisive influence on reducing a polymerization threshold value, shortening exposure time, reducing polymerization cost, improving polymerization efficiency of two-photon polymerization, improving processing micro-nano processing precision and the like.
Accordingly, there is a need to provide a two-photon initiator having a large two-photon absorption cross section and high two-photon polymerization efficiency.
Disclosure of Invention
The invention aims to make up the defects in the prior art and provides a coumarin two-photon initiator and a synthesis method and application thereof.
The specific technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides a coumarin two-photon initiator, which has a chemical structural formula as follows:
wherein R is 1 ,R 2 ,R 3 ,R 4 ,R 5 respectively-Ar (-Ar is aryl, refers to any functional group or substituent derived from a simple aromatic ring), phenyl, o-tolyl, 1-naphthyl, 2-naphthyl and the like belong to the category), -X (-X is any one of F, cl, br, I), -H, -OH, -CN, -NO 2 、-NH 2 、-COOC x H 2x+1 、-OC x H 2x+1 、-N(C x H 2x+1 ) 2 、-CH 2 CH(C m H 2m+1 )C n H 2n+1 Wherein x is any natural number in the range of 1 to 15, m+n=5 to 30, m and n are non-zero natural numbers.
In a second aspect, the invention provides a method for synthesizing a coumarin two-photon initiator, which comprises the following steps:
s1: dissolving 2, 5-disubstituted thiophene and aromatic compounds in an organic solvent, adding strong base and palladium catalyst, and reacting for 1-72 hours at-100-150 ℃ in an inert gas atmosphere; after the reaction is finished, the reaction returns to room temperature, and then is sequentially extracted, washed, dried, filtered and purified to obtain R 1 First product being an-Ar group (if R 1 Halogen, carbon chain or other simple groups, the step can be omitted, and the raw materials with the groups can be directly purchased;
s2: dissolving the first product in an organic solvent, then adding an ester compound and sodium hydride, and reacting for 1-50 hours at the temperature of-20-100 ℃; after the reaction is finished, the reaction returns to room temperature, and then the second product is obtained after extraction, cleaning, drying, filtering and purification are sequentially carried out;
s3: dissolving the second product, the Lewis base and the salicylaldehyde derivative in an organic solvent, and reacting for 1-64 hours at 0-150 ℃ in an anhydrous and anaerobic environment; and (3) after the reaction is finished, recovering the temperature to room temperature, and then sequentially extracting, cleaning, drying, filtering and purifying to obtain the coumarin two-photon initiator.
Preferably, the steps of extraction, washing, drying, filtration and purification are specifically as follows: extraction with Dimethylformamide (DCM), washing several times, combining the organic phases, followed by addition of anhydrous Na 2 SO 4 Drying, filtering, and purifying the crude product obtained after filtering by column chromatography.
Preferably, in the step S1, the molar ratio of the 2, 5-disubstituted thiophene to the aromatic compound is 1:1 to 1:8.
Preferably, the molar ratio of the aromatic compound, the palladium catalyst and the strong base is 1 (0.01-1): 1-10.
Preferably, the aromatic compound is any one or a mixture of two or more of phenylboronic acid, phenylboronic anhydride, pentafluorophenylboronic acid, 4-fluorobenzeneboronic acid, 2-fluorobenzeneboronic acid, 4-chlorophenylboronic acid, sodium tetraphenylborate, 2-naphthylboronic acid, 2-biphenylboronic acid, 3-bromophenylboronic acid, 4-biphenylboronic acid, 3-biphenylboronic acid, 4-tolueneboronic acid, m-butylphenylboronic acid, 3-nitrobenzeneboronic acid, 4-cyanobenzeneboronic acid, 3-aminophenylboronic acid, 4-carboxyphenylboronic acid, 4-propylphenylboronic acid, 4-acetylphenylboronic acid, 2-vinylphenylboronic acid, 4-triphenylamine borate, p-ethoxyphenylboronic acid, 4-ethylphenylboronic acid, 4-nonylphenylphenylboronic acid, 3-hydroxyphenylboronic acid pinacol ester, 4-butoxyphenylboronic acid, 4-benzyloxy phenylboronic acid, 4-hexyloxybenzeneboronic acid, 4-octyloxybenzeneboronic acid, 4-cyclohexylphenylboronic acid, 4-pentyloxyphenylboronic acid, and the like.
Preferably, the palladium catalyst is one or a mixture of more than two of bis (tri-tert-butylphosphine) palladium, tetrakis (triphenylphosphine) palladium, palladium acetate, diphenylphosphino ferrocene palladium dichloride, dichlorodiphenylphosphino palladium, palladium carbon, palladium pivalate, trifluoroacetate palladium and tris (dibenzylideneacetone) dipalladium.
Preferably, in the step S2, the molar ratio of the first product, the ester compound and the sodium hydride is 1 (2-8): 2-8, more preferably 1 (2-6): 2-6.
Preferably, the ester compound is any one or a mixture of two or more of methyl acetate, ethyl acetate, butyl acetate, ethyl propionate, phenyl acetate, methyl benzoate, ethyl caproate, ethyl trimethylacetate, diethyl malonate, ethyl pyruvate, ethyl laurate, octyl acrylate, diethyl oxaloacetate, tetraethyl orthocarbonate, ethyl isohexanoate, diethyl carbonate, ethyl tridecanoate, ethyl pentadecanoate, ethyl benzoylacetate, diethyl phthalate, ethyl 2-chloroacetoacetate, ethyl isobutyrate, and diethyl glutarate.
Preferably, in the step S3, the molar ratio of the second product, the Lewis base and the salicylaldehyde derivative is 1 (1-8): 1-8.
Preferably, the lewis base is any one or a mixture of more than two of quaternary ammonium salt, pyridine, aniline, triethylamine, diethylamine, potassium tert-butoxide, sodium alkoxide, sodium hydride, lithium diisopropylamide, piperidine, 4-dimethylpyridine and quinoline.
Preferably, the salicylaldehyde derivative is that the substituent at the 4-position of salicylaldehyde is-H, -X, -CN, -OH, -NO 2 、-NH 2 、-COOC x H 2x+1 、-OC x H 2x+1 、-N(C x H 2x+1 ) 2 -any one of Ar, wherein, -X is any one of F, cl, br, I, X is any natural number in the range of 1 to 15.
Preferably, the organic solvent is one or a mixture of two or more of methanol, ethanol, isopropanol, diethyl ether, diethanol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, γ -butyrolactone, di (ethylene glycol) diethyl ether, methyl iso Ding Tonger ethanol monoethyl ether, acetone, dichloromethane, chloroform, N-hexane, toluene, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, acetic acid and acetic anhydride.
Preferably, steps S2 and S3 are both performed in an anhydrous and anaerobic environment; the inert gas is any one of helium, neon, argon, krypton, xenon, radon and nitrogen.
In a third aspect, the invention provides an application of the coumarin two-photon initiator in the micro-nano processing and photoresist fields.
Compared with the prior art, the invention has the following beneficial effects:
1) According to the two-photon initiator molecule, a thiophene ring is used as a core, coumarin is used as an arm, and the solubility and the two-photon polymerization efficiency of the series of initiators in the resin are improved by introducing aromatic rings, carbon chains and electron-withdrawing groups on the thiophene core and the coumarin arm.
2) The two-photon initiator has a larger two-photon absorption section, good stability and two-photon polymerization activity, and high microstructure precision processed by two-photon polymerization reaction.
Drawings
FIG. 1 is a graph of the Z-Scan test results of the two-photon initiator prepared in example 2;
FIG. 2 is a line matrix electron microscopic image of the photoresist obtained in example 3 after development by femtosecond laser lithography;
FIG. 3 is an electron microscope image of a 3D model of the photoresist obtained in example 4 after being developed by a femtosecond laser printer;
FIG. 4 is a graph showing the nuclear magnetic resonance results of the product obtained in example 1;
FIG. 5 is a graph showing the nuclear magnetic resonance results of the product obtained in example 2.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments and the accompanying drawings. Those skilled in the art will appreciate that these embodiments are by way of example only. Numerous variations, changes, and substitutions will now occur to those skilled in the art without departing from the invention. It should be understood that various alternatives to the embodiments of the invention described in the specification may be employed in practicing the invention. The appended claims are intended to define the scope of the invention and are therefore to cover methods and structures within the scope of these claims and their equivalents. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The manufacturer reagents or instruments are not noted and are all conventional products available commercially.
Example 1
The two-photon initiator is prepared by the embodiment, and the specific synthesis method comprises the following steps:
step one:
to the pressure-resistant flask was added 2-acetyl-5-bromothiophene (1 g,4.88 mmol), phenylboronic acid (0.89 g,7.32 mmol), tetrakis (triphenylphosphine) palladium (0.552 g,0.49 mmol), anhydrous sodium carbonate (1.03 g,9.76 mmol), and ethylene glycol dimethyl ether and water were added to dissolve, and reacted under anhydrous and anaerobic conditions at 130℃for 12 hours. The reaction process can be as follows:
reaction completionAfter the addition of a suitable amount of water, extraction three times with DCM and the organic phases were combined. Organic phase added anhydrous Na 2 SO 4 Drying, filtering, removing solvent under reduced pressure, purifying by column chromatography, and removing solvent under reduced pressure to obtain light yellow powder of 0.94g of 2-acetyl-5-phenylthiophene with a yield of 95%. The resulting product was characterized by nuclear magnetic resonance and the results were as follows: 1 H NMR(400MHz,CDCl 3 )δ7.40～8.10(m,7H)δ2.50(s,3H,-CH 3 )。
step two:
to the reaction flask, 10ml of diethyl carbonate and sodium hydride (0.29 g,12.0 mmol) were added and stirred for 2 hours in an ice-water bath, followed by dropwise addition of 10ml of a THF solution of 2-acetyl-5-phenylthiophene (0.15 g,0.7 mmol) and reaction at 80℃for 24 hours. The reaction process can be as follows:
after the reaction, cooling to room temperature, adding appropriate amount of glacial acetic acid for acidification, washing with distilled water until no acidity appears, extracting with DCM for three times, mixing organic phases, adding anhydrous Na 2 SO 4 Drying, filtering, removing solvent under reduced pressure, purifying by column chromatography, and removing solvent under reduced pressure to obtain yellow powdery solid 2-diacetoacetic acid ethyl ester-5-phenylthiophene 0.2g, with a yield of 99%. The resulting product was characterized by nuclear magnetic resonance and the results were as follows: 1 H NMR(400MHz,CDCl 3 )δ1.20(m,3H,-CH 3 ),4.11(m,2H,-CH 2 O-),3.84(s,2H,-CH 2 -),7.49～8.00(m,7H)。
step three:
to the reaction flask were added ethyl 2-diacetoacetate-5-phenylthiophene (0.1 g,0.34 mmol), diethylamino salicylic aldehyde (0.116 g,0.60 mmol), triethylamine 0.5ml and 20ml of anhydrous methanol, and the mixture was reacted at 65℃for 5 hours under the protection of argon. The reaction process can be as follows:
after the reaction, adding a large amount of KOH, washing until the reaction does not become alkaline, extracting with DCM for three times, combining organic phases, washing with water for three times, decompressing, desolventizing, purifying by column chromatography to obtain 0.14g of orange-red powdery solid with the yield of 98%. And the nuclear magnetic resonance characterization is carried out on the obtained product, the nuclear magnetic resonance result is shown in fig. 4, and the nuclear magnetic data is consistent with the structure of a preset product, so that the designed molecule is successfully synthesized, and the product has higher purity.
Example 2
The two-photon initiator is prepared by the embodiment, and the specific synthesis method comprises the following steps:
step one:
to the reaction flask, 15ml of diethyl carbonate and 15ml of sodium hydride (3.65 g,0.095 mol) in an ice salt bath were added and stirred for 2 hours, followed by dropwise addition of 15ml of a THF solution of 2-acetylthiophene (3.00 g,23.8 mmol) and reaction at 80℃for 32 hours. The reaction process can be as follows:
after the reaction, cooling to room temperature, adding appropriate amount of glacial acetic acid for acidification, washing with distilled water until no acidity appears, extracting with DCM for three times, mixing organic phases, adding anhydrous Na 2 SO 4 Drying, filtering, removing solvent under reduced pressure, purifying by column chromatography, and removing solvent under reduced pressure to obtain yellow liquid of 4.7g of 2-diacetoacetic acid ethyl thiophene with the yield of 100%. The resulting product was characterized by nuclear magnetic resonance and the results were as follows: 1 H NMR(400MHz,CDCl 3 )δ1.20(m,3H,-CH 3 ),4.11(m,2H,-CH 2 O-),3.84(s,2H,-CH 2 -),7.25(m,1H),7.99(m,2H)。
step three:
to the reaction flask were added 2-diacetoxyethyl thiophene (0.2 g,1.02 mmol), dibutylamino Shui Yang aldehyde (0.3 g,1.22 mmol), triethylamine 0.5ml and 20ml of anhydrous methanol, and the mixture was reacted at 65℃for 30 hours under nitrogen atmosphere. The reaction process can be as follows:
after the reaction, a large amount of KOH is added, the mixture is washed until the mixture does not become alkaline, the mixture is extracted three times by DCM, the organic phases are combined, washed three times by water, decompressed and desolventized, and purified by column chromatography, thus obtaining 0.37g of orange-yellow liquid with the yield of 99%. And the nuclear magnetic resonance characterization is carried out on the obtained product, the nuclear magnetic resonance result is shown in fig. 5, and the nuclear magnetic data is consistent with the structure of a preset product, so that the designed molecule is successfully synthesized, and the product has higher purity. In addition, performance test is carried out on the two-photon initiator obtained in the embodiment, the two-photon absorption section of the initiator is 340GM through the test of a Z-Scan device, and the test result is shown in fig. 1, which shows that the two-photon initiator has larger two-photon absorption capacity.
Example 3
Under the dark environment, 10mg of the two-photon initiator in the embodiment 2 and 400mg of pentaerythritol triacrylate are added into a 10mL beaker and stirred until the two-photon initiator and the pentaerythritol triacrylate are uniformly mixed, and the two-photon photoresist is obtained. The glass slide is smeared with a proper amount of prepared photoresist, micro-nano structure processing is carried out under 780nm titanium sapphire femtosecond laser, the femtosecond laser pulse is 100fs, the laser frequency is 80MHz, a two-dimensional line graph shown in figure 2 is obtained, and from a scanning result, a good line structure can be obtained by using the initiator, and the minimum line width is below 100 nm.
Example 4
Under a dark environment, 10mg of the two-photon initiator in the example 2 and 400mg of pentaerythritol triacrylate are added into a 10mL beaker, and the mixture is stirred until the mixture is uniform, so as to obtain the two-photon photoresist. And (3) smearing a proper amount of prepared photoresist on the glass slide, and processing the micro-nano structure under 780nm titanium sapphire femtosecond laser, wherein the femtosecond laser pulse is 100fs, and the laser frequency is 80MHz. A three-dimensional structure in the form of a thread is obtained, as shown in fig. 3. It can be seen from the figure that the structures processed using the initiator have smooth edges and a stable stereomorphology.
Therefore, the initiator improves the solubility of the two-photon initiator and improves the two-photon absorption section by changing the functional group and the position of the functional group, thereby obtaining more excellent two-photon polymerization initiation efficiency. The synthesis steps of the novel two-photon initiator mainly comprise: step one, introducing different proper groups into the positions 2 and 5 of thiophene; step two, introducing ester groups on the basis of the products of the step one; and thirdly, performing a Kenaonvinguel condensation reaction on the product of the step two and the salicylaldehyde derivative to generate a corresponding novel two-photon initiator. The novel two-photon initiator provided by the invention has higher sensitivity, larger two-photon absorption section and lower polymerization threshold, and shows excellent two-photon polymerization activity and stability.
Compared with the Chinese patent with the application number of 2021112613459, the invention can regulate and control the two-photon absorption capacity and the solubility of the initiator molecule by optimizing the molecular structure, thereby obtaining more excellent two-photon initiation performance.
The above embodiment is only a preferred embodiment of the present invention, but it is not intended to limit the present invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, all the technical schemes obtained by adopting the equivalent substitution or equivalent transformation are within the protection scope of the invention.

Claims (9)

1. The coumarin two-photon initiator is characterized by comprising the following specific chemical structural formula:
2. the synthesis method of the coumarin two-photon initiator is characterized by comprising the following steps of:
s1: dissolving 2-acetylthiophene in an organic solvent, then adding diethyl carbonate and sodium hydride, and reacting for 1-50 hours at the temperature of-20-100 ℃; after the reaction is finished, the temperature is restored to the room temperature, and then the 2-diacetoacetic acid ethyl thiophene is obtained after the steps of extraction, cleaning, drying, filtering and purification are sequentially carried out;
s2: dissolving the 2-diacetoxyethyl thiophene, lewis base and dibutylamino salicylaldehyde in an organic solvent, and reacting for 1-64 hours at 0-150 ℃ in an anhydrous and anaerobic environment; and (3) after the reaction is finished, recovering the temperature to room temperature, and then sequentially extracting, cleaning, drying, filtering and purifying to obtain the coumarin two-photon initiator.
3. The synthesis method of the coumarin two-photon initiator is characterized by comprising the following steps of:
s1: dissolving 2-acetyl-5-phenyl thiophene in an organic solvent, then adding diethyl carbonate and sodium hydride, and reacting for 1-50 hours at the temperature of minus 20-100 ℃; after the reaction is finished, the reaction returns to room temperature, and then the 2-diacetoacetic acid ethyl ester-5-phenylthiophene is obtained after extraction, cleaning, drying, filtering and purification are sequentially carried out;
s2: dissolving the 2-diacetoacetic acid ethyl ester-5-phenyl thiophene, lewis base and diethylamino salicylaldehyde in an organic solvent, and reacting for 1-64 hours at 0-150 ℃ in an anhydrous and anaerobic environment; and (3) after the reaction is finished, recovering the temperature to room temperature, and then sequentially extracting, cleaning, drying, filtering and purifying to obtain the coumarin two-photon initiator.
4. The method for synthesizing the coumarin two-photon initiator according to claim 3, wherein the preparation method of the 2-acetyl-5-phenylthiophene is as follows:
1g,4.88mmol of 2-acetyl-5-bromothiophene, 0.89g,7.32mmol of phenylboric acid, 0.552 g,0.49mmol of tetrakis (triphenylphosphine) palladium, 1.03g,9.76mmol of anhydrous sodium carbonate are added into ethylene glycol dimethyl ether and water for dissolution, and the reaction is carried out for 12 hours under anhydrous and anaerobic conditions at 130 ℃; and after the reaction is finished, the reaction returns to room temperature, and then the first product is obtained after extraction, cleaning, drying, filtering and purification are sequentially carried out.
5. The method for synthesizing a coumarin type two-photon initiator according to claim 4, wherein the steps of extraction, washing, drying, filtering and purification are performedThe method comprises the following steps: extracting with dimethylformamide, adding the washed organic phase to anhydrous Na 2 SO 4 Drying, filtering, and purifying the crude product obtained after filtering by column chromatography.
6. The method for synthesizing a coumarin two-photon initiator according to claim 2 or 3, wherein the lewis base is any one or a mixture of two or more of quaternary ammonium salt, pyridine, aniline, triethylamine, diethylamine, potassium tert-butoxide, sodium alkoxide, sodium hydride, lithium diisopropylamide, piperidine, 4-dimethylpyridine and quinoline.
7. The method for synthesizing a coumarin two-photon initiator according to claim 2 or 3, wherein the organic solvent is any one or a mixture of two or more of methanol, ethanol, isopropanol, diethyl ether, diethanol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, γ -butyrolactone, di (ethylene glycol) diethyl ether, methyl iso Ding Tonger ethanol monoethyl ether, acetone, dichloromethane, chloroform, N-hexane, toluene, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, acetic acid and acetic anhydride.
8. A method for synthesizing a coumarin-based two-photon initiator according to claim 2 or 3, wherein steps S1 and S2 are performed in an anhydrous and anaerobic environment.
9. Use of the coumarin-based two-photon initiator according to claim 1 in micro-nano processing and photoresist fields.
CN202210035676.9A 2022-01-13 2022-01-13 Coumarin two-photon initiator and synthesis method and application thereof Active CN114478500B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004292475A (en) * 2003-03-25 2004-10-21 Fuji Photo Film Co Ltd Two-photon absorption polymerizable composition and method for polymerizing the same
WO2018006530A1 (en) * 2016-07-07 2018-01-11 南方科技大学 Chloro-benzothiadiazole-containing conjugated polymer and preparation method therefor and organic solar cell device
CN110684134A (en) * 2019-10-28 2020-01-14 中国工程物理研究院激光聚变研究中心 Heterocyclic modified two-photon polymerization initiator based on phenothiazine or carbazole and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004292475A (en) * 2003-03-25 2004-10-21 Fuji Photo Film Co Ltd Two-photon absorption polymerizable composition and method for polymerizing the same
WO2018006530A1 (en) * 2016-07-07 2018-01-11 南方科技大学 Chloro-benzothiadiazole-containing conjugated polymer and preparation method therefor and organic solar cell device
CN110684134A (en) * 2019-10-28 2020-01-14 中国工程物理研究院激光聚变研究中心 Heterocyclic modified two-photon polymerization initiator based on phenothiazine or carbazole and preparation method thereof

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