Polycarbonyl enol compound, preparation method thereof and application of polycarbonyl enol compound in synthesis of photoinitiator

Abstract

The invention relates to a multi-carbonyl enol compound which has a structure as shown in a general formula I. The compound has a plurality of carbonyl enol structures. The invention further provides a synthesis method of the compound, the multi-carbon-based enol compound is prepared through an acylation reaction, a Willgerodt-Kindler reaction, a Vilsmeier-Haack-Arnold reaction and a hydrolysis reaction, the intermediate reaction step does not involve a noble metal catalyst, and the synthesis route is economical and efficient. The invention also provides a diazo naphthoquinone photoinitiator prepared by esterification and condensation of the compound as a monomer and diazo naphthoquinone sulfonyl chloride, and an application of the photoinitiator in I-line photoresist configuration. The compound disclosed by the invention is highly symmetrical in structure, has a unique enol interconversion and multi-carbonyl and hydroxyl functional group coexisting structure, and has an extremely wide application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a polycarbonyl enol compound and a preparation method thereof, as well as application in the synthesis of a photoinitiator. Background Art

[0002] Carbonyl enol compounds are a class of compounds that exhibit keto-enol tautomerism. Keto-enol tautomerism is due to the acidic α-protons of carbonyl compounds (such as ketones and aldehydes). These protons can be transferred at different pH values ​​to form two isomers, the keto and enol forms. For simple carbonyl compounds under normal conditions, the equilibrium is usually very favorable to the keto tautomer (for example, acetone is >99.999% of the keto tautomer). The keto tautomer is preferred because it is usually about 45-60 kJ / mol more stable than the enol tautomer, mainly due to the stronger C=O double bond (-749 kJ / mol) than the C=C double bond (-611 kJ / mol). Therefore, it is difficult to obtain a stable enol structure relative to the keto form.

[0003] This patent provides a structure in which the C2 position of malondialdehyde is substituted by aromatic hydrocarbons. Since the two carbonyl groups in this structure are linked by a carbon atom and the carbon atom is also connected to an aromatic group, the two carbonyl groups on the structure can undergo keto-enol tautomerism. The theoretical ratio of malondialdehyde and carbonyl enol structures in this type of compound is 1:2. Since the aromatic group can donate electrons to the middle carbon atom, and a hydrogen bond can be formed between the hydroxyl group and the carbonyl enol structure, the enol structure of this type of compound is more stable. At the same time, a pair of P electrons on the hydroxyl oxygen of the enol enol structure and the π bond in the carbon-carbon double bond form a P-π conjugated system, which biases the charge toward the carbon end to a certain extent, increases the polarity of the hydroxyl oxygen hydrogen bond, and makes it easier for hydrogen to leave (pKa: 10.94). This hydroxyl has higher reactivity than the general alcohol hydroxyl group and can react with diazonaphthoquinonesulfonyl chloride to synthesize I-line photosensitive compounds. Summary of the invention

[0004] In view of the above reasons, the present invention provides a polycarbonyl enol compound and a preparation method thereof. The polycarbonyl enol compound can be used as a precursor to prepare a diazo naphthoquinone sulfonate type photosensitive compound, which can be used for the preparation of I-line photoresist.

[0005] According to the first part of the present invention, a polycarbonyl enol compound is provided, wherein the polycarbonyl enol compound has a structure as shown in the following formula I:

[0006] Formula I wherein X independently represents N, C, Si, a benzene ring, or an aromatic heterocyclic ring; R independently represents hydrogen, a halogen, a C1-C18 alkyl branched or straight chain, an aromatic hydrocarbon, a C2-C10 unsaturated hydrocarbon group, or a C3-C12 cycloalkyl group; n represents an integer between 0 and 2; and m represents an integer between 2 and 4; Furthermore, multiple substituents on X are evenly and symmetrically distributed, including compounds with any of the following structural formulas: ; Furthermore, the polycarbonyl enol compound is selected from at least one of the following structural compounds: ; To achieve the above object, according to the second part of the present invention, a method for preparing a polycarbonyl enol compound is also provided, the preparation method comprising: ; Step A1, grafting acetyl groups onto raw material a through acylation reaction; Step A2, synthesizing a carboxylic acid compound by reacting the acetyl compound with a Willgerodt-Kindler reaction; Step A3, preparing a Vilsmeier-Haack-Arnold reagent, adding a carboxylic acid compound to the Vilsmeier-Haack-Arnold reagent to synthesize an onium salt compound; Step A4, hydrolyzing the onium salt compound to obtain a polycarbonyl enol compound; Wherein X each independently represents N, C, Si, benzene ring and aromatic heterocycle, R each independently represents hydrogen, halogen, C1-C18 alkyl branched or straight chain, aromatic hydrocarbon, C2-C10 unsaturated hydrocarbon group, C3-C12 cycloalkyl group, n represents an integer between 0 and 2, and m represents an integer between 2 and 4.

[0007] Furthermore, in step A1, the molar ratio of raw material a and acetyl chloride is 1:3-8, and more preferably 1:4-6; the reaction is carried out under anhydrous conditions and protected by inert gas, the reaction temperature is 25-55°C, preferably 30-45°C, and the reaction time is 12-48h, preferably 12-18h; the solvent includes at least one of dichloromethane, chloroform, carbon tetrachloride, and carbon disulfide.

[0008] Furthermore, in step A2, the molar ratio of raw material b: sulfur powder: sodium hydroxide is 1:6-16:6-16, and more preferably 1:6-12:6-12; the reaction temperature is 90-160°C, and more preferably 100-140°C; the reaction time is 24-36h, and more preferably 30-36h.

[0009] Further, in step A3, the molar ratio of raw material c:DMF:phosphorus oxychloride is 1:100-200:10-50, and more preferably 1:120-160:30-50; the reaction is carried out under nitrogen protection, the reaction temperature is 90-120 degrees Celsius, and more preferably 100-105 degrees Celsius; the reaction time is preferably 36-48 hours.

[0010] Further, in step A4, the reaction solvent is methanol, and the molar ratio of raw material d: sodium methoxide is 1:10-30, and more preferably 1:20-25; the reaction is carried out under nitrogen protection, the reaction temperature is preferably 35-45°C, and the reaction time is preferably 8-12h.

[0011] Furthermore, the purity of the polycarbonyl enol compound is purified from chemical purity by precipitation after dissolution, chromatographic column separation, recrystallization, etc.

[0012] According to the third part of the present invention, there is also provided the use of the polycarbonyl enol compound as a monomer for esterification condensation with diazonaphthoquinone sulfonyl chloride to prepare diazonaphthoquinone type photoinitiator, wherein the diazonaphthoquinone sulfonate has a structure shown in the following formula II:

[0013] Formula II Wherein X each independently represents N, C, Si, benzene ring and aromatic heterocycle, R each independently represents hydrogen, halogen, C1-C18 alkyl branched or straight chain, aromatic hydrocarbon, C2-C10 unsaturated hydrocarbon group, C3-C12 cycloalkyl group, n represents an integer between 0 and 2, and m represents an integer between 2 and 4.

[0014] Furthermore, the polycarbonyl enol compound and diazonaphthoquinone sulfonyl chloride are mixed in an organic solvent, and an alkaline activator is added to react to obtain the diazonaphthoquinone sulfonate product system.

[0015] The reaction is carried out under an inert gas protective atmosphere, the reaction temperature is 20 to 60° C., preferably 25 to 40° C., and the reaction time is 0.5 to 6 hours, preferably 1 to 3 hours.

[0016] The alkaline activator includes at least one of triethylamine, tripropylamine, ethylenediamine, pyridine, N,N-dimethylaniline, tetramethylammonium hydroxide, sodium methoxide, sodium ethoxide, lithium diisopropylamide, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide, ammonium hydroxide, and sodium hydride, preferably at least one of triethylamine, pyridine, and sodium bicarbonate.

[0017] Further, as a preferred embodiment, the diazonaphthoquinone sulfonate is selected from at least one of the following structural compounds: .

[0018] According to the fourth part of the present invention, the application of the diazonaphthoquinone type photoinitiator in I-line photoresist configuration is also provided, and the photoinitiator is any one of the diazonaphthoquinone sulfonates provided in the third part or the diazonaphthoquinone ester obtained according to any one of the preparation methods provided in the fourth part.

[0019] Furthermore, the mass proportion of the diazonaphthoquinone sulfonate in the photoresist composition is 0.1-5.0%; more preferably, the mass proportion is 0.5-1.0%. Furthermore, it is preferred that the resin is a phenolic resin, and the weight average molecular weight Mw of the phenolic resin is 2,000 to 40,000.

[0020] The polycarbonyl enol compound and the preparation method thereof provided by the present invention are used to prepare a naphthoquinone sulfonate type photosensitive compound, and the photosensitive compound can be used to prepare an I-line photoresist with good performance. DETAILED DESCRIPTION

[0021] The technical solution of the present invention is further explained below in conjunction with specific embodiments. It is worth noting that the following embodiments are only preferred embodiments of the present invention and should not be construed as limiting the present invention. The protection scope of the present invention shall be subject to the contents recorded in the claims. Any modification or replacement made by a person skilled in the art to the technical solution of the present invention without creative work shall fall within the protection scope of the present invention.

[0022] In a first typical embodiment of the present application, the present application provides a polycarbonyl enol compound, wherein the polycarbonyl enol compound has a structure as shown in the following formula I:

[0023] Formula I Wherein X each independently represents N, C, Si, a benzene ring and an aromatic heterocycle, R each independently represents hydrogen, a halogen, a C1-C18 alkyl branched or straight chain, an aromatic hydrocarbon, a C2-C10 unsaturated hydrocarbon group, a C3-C12 cycloalkyl group, n represents an integer between 0 and 2, m represents an integer between 2 and 4, and multiple substituents on X are evenly and symmetrically distributed.

[0024] By applying the scheme provided in the present invention application, the multi-carbonyl enol compound can be used as a precursor to prepare a naphthoquinone sulfonate-type photosensitive compound, and the photosensitive compound can be used to prepare an I-line photoresist with good performance.

[0025] In some embodiments of the present application, the polycarbonyl enol compound is selected from at least one of the following structural compounds: .

[0026] To achieve the above object, in a second typical embodiment of the present invention, a method for synthesizing a polycarbonyl enol compound is also provided, the method comprising: ; Step A1, grafting acetyl groups onto raw material a through acylation reaction; Step A2, synthesizing a carboxylic acid compound by subjecting the acetyl compound to a Willgerodt-Kindler reaction; Step A3, preparing a Vilsmeier-Haack-Arnold reagent, adding a carboxylic acid compound to the Vilsmeier-Haack-Arnold reagent to synthesize an onium salt compound; Step A4, hydrolyzing the onium salt compound to obtain a polycarbonyl enol compound; X, R, m, n and the polycarbonyl enol compound have the same meanings as in the first exemplary embodiment described above.

[0027] By applying the technical solution of the present application, the preparation method of the polycarbonyl enol compound provided by the present application has a reasonable process route, is simple and safe to operate, is green and efficient, economical and environmentally friendly, and is easy to realize industrial large-scale production.

[0028] In order to further improve the yield and preparation efficiency of polycarbonyl enol compounds and save production energy consumption and costs, the following optimizations were made to the various synthesis conditions involved in the synthesis route: Furthermore, in step A1, the molar ratio of raw material a and acetyl chloride is 1:3-8, and more preferably 1:4-6; the reaction is carried out under anhydrous conditions and protected by inert gas, the reaction temperature is 25-55°C, preferably 30-45°C, and the reaction time is 12-48h, preferably 12-18h; the solvent includes at least one of dichloromethane, chloroform, carbon tetrachloride, and carbon disulfide.

[0029] Furthermore, in step A2, the molar ratio of raw material b: sulfur powder: sodium hydroxide is 1:6-16:6-16, and more preferably 1:6-12:6-12; the reaction temperature is 90-160°C, and more preferably 100-140°C; the reaction time is 24-36h, and more preferably 30-36h.

[0030] Further, in step A3, the molar ratio of raw material c:DMF:phosphorus oxychloride is 1:100-200:10-50, and more preferably 1:120-160:30-50; the reaction is carried out under nitrogen protection, the reaction temperature is 90-120 degrees Celsius, and more preferably 100-105 degrees Celsius; the reaction time is preferably 36-48 hours.

[0031] Further, in step A4, the reaction solvent is methanol, and the molar ratio of raw material d: sodium methoxide is 1:10-30, and more preferably 1:20-25; the reaction is carried out under nitrogen protection, the reaction temperature is preferably 35-45°C, and the reaction time is preferably 8-12h.

[0032] Furthermore, the purity of the polycarbonyl enol compound is purified from chemical purity by precipitation after dissolution, chromatographic column separation, recrystallization, etc. In a third typical embodiment of the present application, there is also provided an application of the compound as a monomer for esterification and condensation with diazonaphthoquinone sulfonyl chloride to prepare a diazonaphthoquinone type photoinitiator, wherein the diazonaphthoquinone sulfonate has a structure shown in the following formula II:

[0033] Formula II wherein X, R, m, n and the polycarbonyl enol compound have the same meanings as in any one of claims 1 to 3 above.

[0034] Furthermore, the diazonaphthoquinone sulfonate is selected from at least one of the following structural compounds: .

[0035] In a fourth typical embodiment of the present invention, the use of the naphthoquinone diazo type photoinitiator in the I-line photoresist configuration is also provided, wherein the photoinitiator is any one of the naphthoquinone diazo sulfonates provided in the third part above; Further, the mass proportion of the diazonaphthoquinone sulfonate in the photoresist composition is 0.5-5.0%; Furthermore, it is preferred that the resin is a phenolic resin, and the weight average molecular weight Mw of the phenolic resin is 2,000 to 40,000.

[0036] In some embodiments of the present application, in the process of preparing photoresist using the above-mentioned photoresist composition, phenolic resin and photosensitizer are dispersed in propylene glycol methyl ether acetate to facilitate the preparation of photoresist with stable performance.

[0037] By applying the scheme provided in the present application and adopting the polycarbonyl enol compound and the preparation method thereof provided in the invention, the compound can be used as a monomer for esterification condensation with diazonaphthoquinone sulfonyl chloride to prepare diazonaphthoquinone type photoinitiator, and the photoinitiator can be used in I-line photoresist configuration.

[0038] The beneficial effects of the present application will be further described below with reference to embodiments.

[0039] Example 1 This embodiment provides a method for preparing a polycarbonyl enol compound, and the preparation reaction is shown as follows: ; The specific steps include: A1 First add 4.2 g acetyl chloride and 6.8 g anhydrous aluminum chloride to 40 ml carbon disulfide and stir magnetically. Then dissolve 2.5 g triphenylmethane in 10 ml carbon disulfide and drip into the reaction solution at a uniform speed with a constant pressure funnel. The solution gradually turns dark brown. React for 18 hours, let stand and cool to room temperature, pour off the supernatant, and a large amount of dark brown solid is attached to the bottom of the bottle. Add 100 g crushed ice, 25 ml concentrated hydrochloric acid, and 100 ml dichloromethane in sequence, and stir until all the solids are dissolved. Add the resulting solution to a separatory funnel, extract with 50 ml x 3 dichloromethane, add 3 spoons of anhydrous magnesium sulfate to the resulting dichloromethane solution and stir evenly. Filter to obtain an anhydrous solution, spin out dichloromethane to obtain 4.3 g brown solid, with a yield of 96%; A2 3.8 g of triacetyltriphenylmethane, 2 g of sulfur and 50 ml of morpholin were added to a three-necked flask. Under nitrogen protection, a heating jacket was used to react at 140°C for 18 hours (the color changes from orange to black, with white smoke, and someone needs to be on duty). After turning off the heating jacket, cool it down, add 50 ml of 1,4-dioxane, and react at room temperature for 30 minutes. Pour the reaction solution into a beaker filled with a large amount of water, and a light yellow precipitate will appear immediately. Filter and wash. Add the filtered solid to 23g of sodium hydroxide, 50ml, and 50ml of ethanol, and react at 100°C for 16 hours (the color becomes darker). Add hydrochloric acid to pH=1 and filter to obtain a solid. Add sodium hydroxide solution to dissolve, then add hydrochloric acid to precipitate, and filter. Repeat several times. Remove impurities to obtain 4.9 g of red powder with a yield of 92%.

[0040] A3 In an ice bath, in a three-necked flask, under magnetic stirring, use a constant pressure funnel to slowly and uniformly drip 20 ml of DMF into 3 ml of phosphorus oxychloride. After dripping, react for 30 minutes. Transfer the prepared Weismeier reagent into an oil bath pot, add 0.838 g of triphenylbenzene triacetate, pass nitrogen protection, and react at 100 degrees Celsius for 2 days. Cool and add crushed ice to decompose excess Weismeier reagent. Add an aqueous solution containing 8 g of sodium perchlorate, stir and let stand or refrigerate. Filter to obtain a brown-yellow powder.

[0041] A4 Dissolve all sodium methoxide in methanol under ice bath conditions and react for about 10 minutes. Transfer the solution to an oil bath, add triphenylbenzenium salt for hydrolysis, protect with nitrogen, and react at 40 degrees Celsius for 10-12 hours. After cooling, add hydrochloric acid or glacial acetic acid to pH=1, and extract with dichloromethane. Add anhydrous magnesium sulfate to remove water, filter, and stand for dichloromethane to evaporate. Obtain a yellow solid with a yield of 86%. The structure of the product S1 was confirmed by hydrogen and carbon nuclear magnetic resonance spectra, and the specific characterization results are as follows: 1 H NMR (500 MHz, (CD 3 ) 2 SO) δ 9.52 (d, J = 1.3 Hz, 3H), 7.68 (dd, J = 5.5,1.3 Hz, 3H), 7.39 – 7.30 (m, 12H), 5.22 (q, J = 0.9 Hz, 1H). 13 C-NMR ((CD 3 ) 2 SO, 125 MHz) δ190.21, 190.17, 172.16, 172.12, 139.92,139.89, 134.05, 134.02, 134.00, 133.99, 128.29, 128.26, 128.23, 127.75,127.73, 127.70, 127.68, 120.86, 120.81, 120.76, 55.76. Example 2 This embodiment provides a method for preparing a polycarbonyl enol compound, and the preparation reaction is shown as follows: ; The difference between the preparation method of Example 2 and that of Example 1 is that the raw material Y1 is replaced by the raw material M1, the other reaction substrates are changed in proportion according to the feed ratio, and the other conditions remain unchanged. A yellow-brown solid S2 is obtained, and the overall yield is 63%. The structure of the product S2 is confirmed by nuclear magnetic resonance hydrogen spectrum, and the specific characterization results are as follows: 1 H NMR (500 MHz, (CD 3 ) 2 SO) δ 9.47 (d, J = 1.3 Hz, 2H), 7.69 (dd, J= 5.6,1.4 Hz, 2H), 7.29 – 7.24 (m, 4H), 7.09 – 7.03 (m, 4H), 1.38 (s, 9H). 13 C-NMR ((CD 3 ) 2 SO, 125 MHz) δ 190.04, 190.00, 172.17, 172.16, 172.12,172.11, 145.50, 129.50, 129.48, 129.45, 129.44, 129.43, 126.81, 126.76,126.75, 121.74, 121.69, 118.83, 118.82, 118.81, 118.80, 118.79, 118.78,118.76, 57.57, 27.66. Example 3 This embodiment provides a method for preparing a polycarbonyl enol compound, and the preparation reaction is shown as follows: ; The preparation method of Example 3 is different from that of Example 1 in that the raw material Y1 is replaced by the raw material A1, and the other reaction substrates are changed in proportion according to the feed ratio, and the other conditions remain unchanged. A yellow-brown solid S3 is obtained, and the overall yield is 58%. The structure of the product S3 is confirmed by nuclear magnetic resonance hydrogen spectrum, and the specific characterization results are as follows: 1 H NMR (500 MHz, (CD 3 ) 2 SO) δ 9.52 (d, J = 1.3 Hz, 2H), 7.93 (t, J = 2.2Hz, 1H), 7.85 – 7.78 (m, 4H), 7.68 (dd, J = 5.5, 1.3 Hz, 2H), 7.47 – 7.40 (m,4H), 7.39 – 7.35 (m, 2H), 2.85 – 2.75 (m, 1H), 1.81 – 1.65 (m, 4H), 1.62 –1.37 (m, 7H). 13 C-NMR ((CD 3 ) 2SO, 125 MHz)δ 192.72, 146.51, 138.06, 137.56, 137.32,136.92, 128.91, 128.46, 128.31, 126.81, 123.30, 42.45, 34.19, 26.66, 26.42. Example 4 This embodiment provides a method for preparing a polycarbonyl enol compound, and the preparation reaction is shown as follows: ; The difference between the preparation method of Example 4 and that of Example 1 is that the raw material Y1 is replaced by the raw material N1, and the other reaction substrates are changed in proportion according to the feed ratio, and the other conditions remain unchanged. A yellow-brown solid S4 is obtained, and the overall yield is 58%. The structure of the product S4 is confirmed by nuclear magnetic resonance hydrogen spectrum, and the specific characterization results are as follows: 1 H-NMR ((CD 3 ) 2 SO, 500 MHz) δ 9.52 (d, J = 1.3 Hz, 3H), 8.27 – 8.21 (m,6H), 7.66 (dd, J = 5.5, 1.3 Hz, 3H), 7.60 – 7.53 (m, 6H). 13 C-NMR ((CD 3 ) 2 SO, 125 MHz) δ 190.21, 190.17, 171.79, 171.78, 171.75,167.40, 136.15, 136.14, 136.09, 136.08, 131.07, 129.59, 129.58, 129.56,129.55, 129.53, 127.55, 127.53, 127.53, 127.50, 127.48, 121.13. Example 5 This embodiment provides a method for preparing a polycarbonyl enol compound, and the preparation reaction is shown as follows: ; The preparation method of Example 5 is different from that of Example 1 in that the raw material Y1 is replaced by the raw material W1, and the other reaction substrates are changed in proportion according to the feed ratio, and the other conditions remain unchanged. A yellow-brown solid S5 is obtained, and the overall yield is 52%. The structure of the product S5 is confirmed by nuclear magnetic resonance hydrogen spectrum, and the specific characterization results are as follows: 1 H-NMR ((CD 3 ) 2 SO, 500 MHz) δ 9.52 (d, J = 1.3 Hz, 3H), 7.68 (dd, J = 5.5,1.3 Hz, 3H), 7.40 – 7.29 (m, 12H), 1.97 (s, 3H). 13 C-NMR ((CD 3 ) 2 SO, 125 MHz) δ 190.21, 190.17, 172.16, 172.12, 172.11,144.98, 144.95, 134.28, 134.23, 134.21, 128.01, 127.99, 127.97, 127.95,120.81, 56.19, 56.18, 29.79, 29.78, 29.76, 29.74. Example 6 This embodiment provides a method for preparing a polycarbonyl enol compound, and the preparation reaction is shown as follows: ; The difference between the preparation method of Example 6 and that of Example 1 is that the raw material Y1 is replaced by the raw material B1, and the other reaction substrates are changed in proportion according to the feed ratio, and the other conditions remain unchanged. A yellow-brown solid S10 is obtained, and the overall yield is 49%. The structure of the product S10 is confirmed by nuclear magnetic resonance hydrogen spectrum, and the specific characterization results are as follows: 1 H-NMR ((CD 3 ) 2 SO, 500 MHz) δ 9.52 (d, J = 1.3 Hz, 3H), 7.69 (dd, J = 5.6,1.4 Hz, 3H), 7.64 – 7.58 (m, 6H), 7.26 – 7.20 (m, 6H), 3.68 (s, 1H). 13 C-NMR ((CD 3 ) 2SO, 125 MHz) δ 190.21, 190.17, 171.79, 171.78, 171.75,135.77, 135.76, 135.72, 135.71, 135.42, 135.40, 135.39, 135.38, 135.36,135.35, 132.07, 126.22, 126.20, 126.17, 126.15, 120.81, 97.93, 85.77. Example 7 This embodiment provides a method for preparing a polycarbonyl enol compound, and the preparation reaction is shown as follows: ; The difference between the preparation method of Example 7 and that of Example 1 is that the raw material Y1 is replaced by the raw material C1, and the other reaction substrates are changed in proportion according to the feed ratio, and the other conditions remain unchanged. A yellow-brown solid S7 is obtained, and the overall yield is 61%. The structure of the product S7 is confirmed by nuclear magnetic resonance hydrogen spectrum, and the specific characterization results are as follows: 1 H-NMR ((CD 3 ) 2 SO, 500 MHz) δ 9.52 (d, J = 1.3 Hz, 2H), 7.95 (d, J = 2.1Hz, 2H), 7.82 – 7.76 (m, 4H), 7.70 – 7.63 (m, 4H), 7.47 (d, J = 6.7 Hz, 2H),7.44 – 7.38 (m, 4H), 4.14 – 4.07 (m, 2H), 1.74 (p, J = 8.4 Hz, 2H), 1.39 (tq, J =8.3, 4.7 Hz, 2H), 0.93 (t, J = 4.8 Hz, 3H). 13 C-NMR ((CD 3 ) 2 SO, 125 MHz) δ 192.72, 144.61, 144.46, 139.99, 138.13,137.56, 128.91, 127.53, 127.11, 125.66, 123.82, 123.38, 113.41, 43.73, 32.84,19.86, 13.70. Example 8 This embodiment provides a method for preparing a polycarbonyl enol compound, and the reaction formula for its preparation is as follows: ; The difference between the preparation method of Example 8 and that of Example 1 is that the raw material Y1 is replaced by the raw material E1, and the other reaction substrates are changed in proportion according to the feed ratio, and the other conditions remain unchanged. A yellow-brown solid S9 is obtained, and the overall yield is 64%. The structure of the product S9 is confirmed by nuclear magnetic resonance hydrogen spectrum, and the specific characterization results are as follows: 1 H-NMR ((CD 3 ) 2 SO, 500 MHz) δ 9.39 (d, J = 1.3 Hz, 2H), 7.69 (dd, J = 5.6,1.4 Hz, 2H), 7.36 – 7.30 (m, 4H), 7.10 – 7.04 (m, 4H), 4.70 (d, J = 10.8 Hz,1H), 4.64 (d, J = 10.8 Hz, 1H), 2.74 (s, 1H). 13 C-NMR ((CD 3 ) 2 SO, 125 MHz) δ 190.88, 190.84, 172.17, 172.12, 147.61,129.65, 129.64, 129.60, 129.59, 129.58, 126.67, 126.61, 120.65, 116.40,116.38, 116.36, 116.35, 116.33, 116.31, 86.98, 74.12, 74.09, 38.61, 38.59. Example 9 This embodiment provides a method for preparing a polycarbonyl enol compound, and the reaction formula for its preparation is as follows: ; The difference between the preparation method of Example 9 and that of Example 1 is that the raw material Y1 is replaced by the raw material F1, the other reaction substrates are changed in proportion according to the feed ratio, and the other conditions remain unchanged. A yellow-brown solid S17 is obtained with a comprehensive yield of 52%. The structure of the product S17 is confirmed by nuclear magnetic resonance hydrogen spectrum, and the specific characterization results are as follows: 1 H-NMR ((CD 3 )2 SO, 500 MHz) δ 9.52 (d, J = 1.3 Hz, 2H), 7.71 – 7.63 (m,4H), 7.39 (t, J = 1.3 Hz, 1H), 7.39 – 7.34 (m, 5H), 7.34 – 7.28 (m, 4H), 5.36(hept, J = 0.9 Hz, 1H). 13 C-NMR ((CD 3 ) 2 SO, 125 MHz) δ 190.21, 190.17, 172.16, 172.12, 139.96,139.93, 139.78, 139.75, 134.06, 134.05, 134.00, 133.99, 130.50, 128.34,128.32, 128.31, 128.30, 128.29, 128.28, 128.26, 128.25, 128.24, 128.23,127.75, 127.74, 127.73, 127.69, 126.11, 126.08, 126.07, 124.34, 124.31,120.86, 120.81, 120.76, 56.76, 56.73, 56.69, 56.66. Example 10 This embodiment provides a method for preparing naphthoquinone diazosulfonate P1. The preparation reaction formula is shown below. The specific steps include: ; Under the protection of an inert gas atmosphere, 15 g of raw material S1 and 17 g of diazonaphthoquinone compound D1 were dissolved in 250 ml of 1,4-dioxane, the reaction temperature was maintained at 30-35 °C, and then 10 g of triethylamine was slowly added dropwise within 1 h. The mixture was allowed to mature for 1 h, and then 1.0-1.5 wt% dilute hydrochloric acid was slowly added. After filtration, the filtrate was added to 800 ml of ultrapure water. After filtration, the filter cake was filtered and dried to obtain a light yellow solid product P1 of 31 g in total. The effective content of the ester was 99.2% by HPLC, and the yield was about 97.0%.

[0042] Embodiment 11 This embodiment provides a method for preparing naphthoquinone diazosulfonate P2, and the reaction formula for its preparation is as follows: ; The difference between the preparation method of this embodiment and that of embodiment 10 is that the raw material S1 is replaced by the raw material S2, the diazonaphthoquinone is changed in proportion according to the feed ratio, and other conditions remain unchanged. A light yellow solid product P2 is obtained, and the effective content of the esterified product measured by HPLC is 99.1%, and the yield is 95.7%.

[0043] Example 12 This embodiment provides a method for preparing naphthoquinone diazosulfonate P3, and the reaction formula for its preparation is as follows: ; The difference between the preparation method of this embodiment and that of embodiment 10 is that the raw material S1 is replaced by the raw material S5, the diazonaphthoquinone is changed in proportion according to the feed ratio, and other conditions remain unchanged. A light yellow solid product P3 is obtained, and the effective content of the esterified product measured by HPLC is 98.9%, and the yield is 96.3%.

[0044] Embodiment 13 This embodiment provides a method for preparing naphthoquinone diazosulfonate P7, and the reaction formula for its preparation is as follows: ; The difference between the preparation method of this embodiment and that of embodiment 10 is that the raw material S1 is replaced by the raw material S7, the diazonaphthoquinone is changed in proportion according to the feed ratio, and other conditions remain unchanged. A light yellow solid product P7 is obtained, and the effective content of the esterified product measured by HPLC is 99.0%, and the yield is 96.8%.

[0045] Embodiment 14 This embodiment provides a method for preparing naphthoquinone diazosulfonate P10, and the reaction formula for its preparation is as follows: ; The difference between the preparation method of this embodiment and that of embodiment 10 is that the raw material S1 is replaced by the raw material S10, the diazonaphthoquinone is changed in proportion according to the feed ratio, and other conditions remain unchanged. A light yellow solid product P10 is obtained, and the effective content of the esterified product measured by HPLC is 99.2%, and the yield is 95.4%.

[0046] Embodiment 15 The compound P19 (2,3,4,4'-tetrahydroxybenzophenone-2,1,5-diazonaphthoquinone sulfonate, a commercial product) was tested respectively, and the diazonaphthoquinone sulfonates P1-P3, P7 and P10 provided in the above Examples 10-14 were mixed with resin, surfactant, adhesion promoter and solvent as photosensitizers to form photoresist solutions. The photoresist solution was 100 parts by mass, and the solvent was 86 parts, the resin was 11 parts, the surfactant was 0.5 parts, the adhesion promoter was 1.0 parts, and the photosensitizer was 1.5 parts. Among them, the resin was a linear phenolic resin with an average molecular weight of 6000; the solvent was propylene glycol methyl ether acetate; the surfactant was a perfluorinated surfactant; and the adhesion promoter was a melamine adhesive.

[0047] The above-mentioned photoresist solutions are respectively coated on silicon wafers by spin coating, and after vacuum drying, they are baked on a hot plate at a temperature of 110°C for 90 seconds to form a photoresist coating with a coating thickness of about 1.5μm. Then a mercury lamp is used as a light source to expose the photoresist coating, and the total exposure energy is between 200 and 400mJ / cm2. After exposure, it is developed with a tetramethylammonium hydroxide aqueous solution with a mass concentration of 2.38wt%, and the development time is 20s. After washing with water for 30s, it is dried to remove the exposed part to form a photoresist pattern. The photoresist pattern is inspected using a scanning electron microscope to compare the resolution of the photoresist. The resolution is based on the minimum line width that can be achieved. The resolutions of different photoresist patterns are shown in Table 1: Table 1

[0048] Compared with the P19 composition using 2,3,4,4'-tetrahydroxybenzophenone-2,1,5-diazonaphthoquinone sulfonate as a photosensitizer, the photoresist prepared by using the diazonaphthoquinone sulfonate provided in Examples 10-14 has a higher resolution of the pattern formed after exposure and development when applied to the photoresist composition.

[0049] Example 16 The silicon wafer with the photoresist pattern prepared in Comparative Example 1 was cut into several samples, and placed on a heating plate at 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, and 160°C for baking, and the baking time was set to 2 minutes. After baking, after the sample was naturally cooled to room temperature, the cross section of each photoresist pattern was observed with an optical microscope, and the angle between the side wall of the photoresist and the substrate was measured. When the angle was less than 70°, this temperature was regarded as the deformation starting temperature, that is, the heat resistance temperature of the photoresist. The results are shown in Table 2.

[0050] Table 2

[0051] Compared with the P19 composition using 2,3,4,4'-tetrahydroxybenzophenone-2,1,5-diazonaphthoquinone sulfonate as a photosensitizer, the photoresist prepared by using the diazonaphthoquinone sulfonate provided in Examples 10-14 has a higher heat resistance temperature when applied to the photoresist composition.

Claims

1. A polycarbonyl enol compound, characterized in that: The polycarbonyl enol compound has a structure as shown in the following formula I:

2. Formula I Wherein X each independently represents N, C, Si, benzene ring and aromatic heterocycle, R each independently represents hydrogen, halogen, C1-C18 alkyl branched or straight chain, aromatic hydrocarbon, C2-C10 unsaturated hydrocarbon group, C3-C12 cycloalkyl group, n represents an integer between 0 and 2, and m represents an integer between 2 and 4.

3. The polycarbonyl enol compound according to claim 1, characterized in that Multiple substituents on X are evenly and symmetrically distributed; 。 4. The polycarbonyl enol compound according to claim 1, characterized in that The polycarbonyl enol compound is selected from at least one of the following structural compounds: 。 5. A method for preparing a polycarbonyl enol compound according to any one of claims 1 to 3, characterized in that: The preparation method comprises the following steps:

6. Step A1, synthesizing an acetyl compound by acylation reaction of raw material a; Step A2, synthesizing a carboxylic acid compound by Willgerodt-Kindler reaction; Step A3, adding a carboxylic acid compound to a Vilsmeier-Haack-Arnold reagent to synthesize an onium salt compound; Step A4, hydrolyzing the onium salt compound to obtain a polycarbonyl enol compound; Wherein X each independently represents N, C, Si, benzene ring and aromatic heterocycle, R each independently represents hydrogen, halogen, C1-C18 alkyl branched or straight chain, aromatic hydrocarbon, C2-C10 unsaturated hydrocarbon group, C3-C12 cycloalkyl group, n represents an integer between 0 and 2, and m represents an integer between 2 and 4.

7. The method for preparing a polycarbonyl enol compound according to claim 4, characterized in that: Step A1, the molar ratio of raw material a to acetyl chloride is 1:3-8, more preferably 1:4-6; the reaction is carried out under anhydrous conditions and protected by inert gas, the reaction temperature is 25-55°C, preferably 30-45°C, the reaction time is 12-48h, preferably 12-18h; the solvent includes at least one of dichloromethane, chloroform, carbon tetrachloride, and carbon disulfide; Step A2, the molar ratio of raw material b: sulfur powder: sodium hydroxide is 1:6-16:6-16, more preferably 1:6-12:6-12; the reaction temperature is 90-160°C, more preferably 100-140°C, and the reaction time is 24-36h, more preferably 30-36h; Step A3, the molar ratio of raw material c: DMF: phosphorus oxychloride is 1:100-200:10-50, more preferably 1:120-160:30-50; the reaction is carried out under nitrogen protection, the reaction temperature is 90-120 degrees Celsius, more preferably 100-105 degrees Celsius; the reaction time is preferably 36-48 hours; Step A4, the reaction solvent is methanol, the molar ratio of raw material d: sodium methoxide is 1:10-30, and more preferably 1:20-25; the reaction is carried out under nitrogen protection, the reaction temperature is preferably 35-45°C, and the reaction time is preferably 8-12h.

8. A method for preparing naphthoquinone diazonium sulfonate using the compound as claimed in any one of claims 1 to 3 as a monomer, characterized in that: The polycarbonyl enol compound and diazonaphthoquinone sulfonyl chloride are mixed in an organic solvent, and an alkaline activator is added to react to obtain the diazonaphthoquinone sulfonate product system.

9. The preparation method according to claim 6, characterized in that: The reaction is carried out under an inert gas protective atmosphere, the reaction temperature is 20 to 60° C., preferably 25 to 40° C., and the reaction time is 0.5 to 6 hours, preferably 1 to 3 hours; The alkaline activator includes at least one of triethylamine, tripropylamine, ethylenediamine, pyridine, N,N-dimethylaniline, tetramethylammonium hydroxide, sodium methoxide, sodium ethoxide, lithium diisopropylamide, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide, ammonium hydroxide, and sodium hydride, preferably at least one of triethylamine, pyridine, and sodium bicarbonate. The organic solvent includes at least one of dichloromethane, tetrahydrofuran, 1,4-dioxane, N,N-dimethylformamide, toluene, acetonitrile, and methanol.

10. Diazonaphthoquinone sulfonate, characterized in that The diazo naphthoquinone sulfonate prepared by the preparation method according to claim 6 or 7 has a structure shown in the following formula II:

11. Formula II Wherein X each independently represents N, C, Si, benzene ring and aromatic heterocycle, R each independently represents hydrogen, halogen, C1-C18 alkyl branched or straight chain, aromatic hydrocarbon, C2-C10 unsaturated hydrocarbon group, C3-C12 cycloalkyl group, n represents an integer between 0 and 2, and m represents an integer between 2 and 4.

12. A use of the diazonaphthoquinone sulfonate as claimed in claim 8 in photoresist preparation, characterized in that: The naphthoquinone diazide ester is used as a photoinitiator to prepare G / I line photoresist.

13. A G / I line photoresist, characterized in that: The raw materials of the G / I line photoresist include the naphthoquinone sulfonate ester and phenolic resin as claimed in claim 9, wherein the addition amount of the naphthoquinone sulfonate ester is 0.1-5.0%.

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