Continuous flow preparation method of photosensitizer

Abstract

The invention provides a continuous flow preparation method of a photosensitizer, the photosensitizer is prepared by using a continuous flow reaction device, and the continuous flow reaction device comprises a reaction unit, a post-treatment unit, a diazotization unit, a chlorination unit and an esterification unit which are communicated in sequence; the preparation method of the photosensitizer comprises the following steps: conveying a reaction raw material to a continuous flow reaction device through a feed port, and enabling the reaction raw material to sequentially flow through a reaction unit and a post-treatment unit to obtain a first reaction liquid; the first reaction liquid sequentially flows through the diazotization unit, the chlorination unit and the esterification unit through the feeding hole to obtain the photosensitizer; reaction raw materials comprise 2-naphthylamine-1, 5-disulfonic acid, solid alkali and a catalyst, the catalyst comprises at least one of 1, 4, 7, 10, 13, 16-hexaoxacyclo-octadecane, 1, 4, 7, 10, 13-pentaoxacyclo-pentadecane and dicyclohexane-18-crown (ether)-6, an esterifying agent comprises at least one of 2, 3, 4-trihydroxy benzophenone and 2, 3, 4, 4-tetrahydroxy benzophenone, and the yield and quality of the photosensitizer are improved.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a continuous flow preparation method of a photosensitizer. Background Art

[0002] Diazo naphthoquinone-based photosensitive agents have the advantages of strong resistance to dry etching, good heat resistance, and convenient degumming, and are widely used in the fields of microelectronics, micromechanics, printing, etc. The number of diazo groups in each diazo naphthoquinone-based photosensitive agent molecule will directly affect the developing characteristics of the photosensitive agent. At present, most diazo naphthoquinone-based photosensitive agents are prepared by esterification reaction between trihydroxybenzophenone and 2,1-diazo naphthoquinone-5-sulfonyl chloride (abbreviated as 215). The content of monoester, diester, and triester in the esterification product directly determines the number of diazo groups, which in turn affects the developing characteristics of the photosensitive agent. At present, in order to ensure the developing characteristics of the photosensitive agent, most of them are subjected to intermittent autoclave reaction, and alkaline catalysts such as triethylamine and 10% sodium carbonate solution are added to the esterification reaction. However, intermittent operation has high labor intensity, is prone to material and energy loss, has high production costs, long production cycles, poor product batch stability, and unstable quality, which greatly reduces production efficiency, product yield and quality. Therefore, how to further improve the yield and quality of photosensitizers is a technical problem that needs to be solved urgently in this field. Summary of the invention

[0003] The present invention provides a continuous flow preparation method of a photosensitizer, which is carried out by using a continuous flow reaction device and limiting the specific type of catalyst, which is beneficial to improving the yield and quality of the photosensitizer. The preparation method is simple and easy to operate, which is beneficial to realizing large-scale production.

[0004] The continuous flow preparation method of the photosensitizer provided by the present invention uses a continuous flow reaction device to prepare the photosensitizer, and the continuous flow reaction device includes a reaction unit, a post-treatment unit, a diazotization unit, a chlorination unit, and an esterification unit connected in sequence;

[0005] The continuous flow preparation method of the photosensitizer comprises the following steps:

[0006] The reaction raw materials are transported to the continuous flow reaction device through the feed port, and flow through the reaction unit and the post-treatment unit in sequence to obtain a first reaction liquid;

[0007] The first reaction liquid flows through the diazotization unit, the chlorination unit, and the esterification unit in sequence through the feed port, and reacts with the sodium nitrite solution, the chlorination agent, and the esterification agent transported to the diazotization unit, the chlorination unit, and the esterification unit in sequence to obtain a photosensitizer;

[0008] The reaction raw materials include 2-naphthylamine-1,5-disulfonic acid, a solid base and a catalyst, the catalyst includes at least one of 1,4,7,10,13,16-hexaoxacyclooctadecane, 1,4,7,10,13-pentacyclopentadecane and dicyclohexane-18-crown-6, and the esterification agent includes at least one of 2,3,4-trihydroxybenzophenone and 2,3,4,4-tetrahydroxybenzophenone.

[0009] The preparation method as described above, wherein the first reaction liquid is transported to a diazotization unit, mixed with a sodium nitrite solution transported to the diazotization unit through a sodium nitrite solution inlet, and subjected to a diazotization reaction, and then subjected to crystallization, filtration, and drying to obtain a diazotization product, and the diazotization product is mixed with ethylene dichloride to obtain a second reaction liquid; the mass ratio of the diazotization product to the ethylene dichloride is 1:(2-3);

[0010] The second reaction liquid is transported to a chlorination unit, mixed with a chlorinating agent transported to the chlorination unit through a chlorinating agent inlet, and subjected to chlorination treatment to obtain a third reaction liquid;

[0011] The third reaction liquid is transported to the esterification unit, mixed with the esterification agent transported to the esterification unit through the esterification agent inlet, and subjected to esterification treatment to obtain a photosensitizer;

[0012] Among them, the molar ratio of the chlorinating agent to 2-diazo-1-naphthoquinone-5-sulfonic acid in the second reaction liquid is (1-1.2):1; the molar ratio of 2-diazo-1-naphthoquinone-5-sulfonyl chloride to the esterifying agent in the third reaction liquid is (3-4):1.

[0013] The preparation method as described above, wherein the solid base comprises at least one of potassium hydroxide and sodium hydroxide; and / or,

[0014] The chlorinating agent includes at least one of HSO3Cl, SOCl2, PCl3, and POCl3.

[0015] The preparation method as described above, wherein the mass content of the catalyst in the 2-naphthylamine-1,5-disulfonic acid is 0.5-2%; and / or,

[0016] The molar ratio of the solid base to the 2-naphthylamine-1,5-disulfonic acid is (2-4):1.

[0017] The preparation method as described above, wherein the feed rate of the 2-naphthylamine-1,5-disulfonic acid and the catalyst is 10.1 to 40.4 g / min; and / or,

[0018] The solid alkali feed rate is 2.64-15.8 g / min; and / or,

[0019] The feeding rate of the sodium nitrite solution is 9.37-56.2 g / min; and / or,

[0020] The feeding rate of the chlorinating agent is 3.23-12.92 g / min; and / or,

[0021] The feed rate of the esterification agent is 1.94-7.76 g / min.

[0022] The preparation method as described above, wherein the temperature in the reaction unit is 200-300° C.; and / or,

[0023] The temperature in the post-processing unit is 10-30° C.; and / or,

[0024] The temperature in the diazotization unit is 0 to 30° C.; and / or,

[0025] The temperature in the chlorination unit is 50-80° C.; and / or,

[0026] The temperature in the esterification unit is 30-60°C.

[0027] The preparation method as described above, wherein the molar ratio of the sodium nitrite solution to the 2-amino-1-naphthol-5-sulfonic acid in the first reaction solution is (1-1.2):1; and / or,

[0028] The mass concentration of the sodium nitrite solution is 10-30%.

[0029] In the preparation method as described above, the reaction unit, post-treatment unit, diazotization unit, chlorination unit and esterification unit each independently include at least one reactor.

[0030] The preparation method as described above, wherein the reaction time of the photosensitizer is ≤30 min;

[0031] The preparation method as described above, wherein the yield of the photosensitizer is ≥60%;

[0032] The preparation method as described above, wherein the content of tris(6-diazo-5-oxo-5,6-dihydro-1-naphthalenesulfonic acid)-4-benzoyl-1,2,3-benzenetriol) ester in the photosensitizer is ≥90%;

[0033] The chemical formula of the tris(6-diazo-5-oxo-5,6-dihydro-1-naphthalenesulfonic acid)-4-benzoyl-1,2,3-benzenetriol ester is shown in Formula 1:

[0034]

[0035] The implementation of the present invention has at least the following beneficial effects:

[0036] The continuous flow preparation method of the photosensitizer provided by the present invention utilizes a continuous flow reaction device for preparation. By continuously inputting the reaction raw materials into the reaction device, the reaction products can be stably and continuously collected, which greatly shortens the reaction time and greatly improves the reaction efficiency. At the same time, by limiting the specific type of the catalyst, it is helpful to improve the yield and quality of the reaction product. The preparation method is simple and easy to operate, which is conducive to large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 is a schematic structural diagram of a continuous flow reaction device in one embodiment of the present invention;

[0038] Figure 2 This is the HPLC spectrum of the final product of Example 2 of the present invention;

[0039] Figure 3 This is the HNMR spectrum of the final product of Example 2. DETAILED DESCRIPTION

[0040] In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0041] The present invention provides a continuous flow preparation method of a photosensitizer, which uses a continuous flow reaction device to prepare the photosensitizer, wherein the continuous flow reaction device comprises a reaction unit, a post-treatment unit, a diazotization unit, a chlorination unit, and an esterification unit connected in sequence; the preparation method of the photosensitizer comprises the following steps: a reaction raw material is transported to the continuous flow reaction device through a feed inlet, and flows through the reaction unit and the post-treatment unit in sequence to obtain a first reaction liquid; the first reaction liquid flows through the diazotization unit, the chlorination unit, and the esterification unit in sequence through the feed inlet, and reacts with the reaction liquid transported to the diazotization unit, the chlorination unit, and the esterification unit in sequence. A sodium nitrite solution, a chlorinating agent and an esterifying agent react to obtain a photosensitizer; the reaction raw materials include 2-naphthylamine-1,5-disulfonic acid, a solid base and a catalyst, the catalyst includes at least one of 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown 6), 1,4,7,10,13-pentacyclopentadecane (15-crown 5) and dicyclohexane-18-crown (ether)-6; the esterifying agent includes at least one of 2,3,4-trihydroxybenzophenone (3HBP) and 2,3,4,4-tetrahydroxybenzophenone (4HBP).

[0042] The reaction unit is used to provide a place for the reaction raw materials to react, the post-treatment unit is used to provide a place for acidification treatment and solid-liquid separation, the diazotization unit is used to provide a place for diazotization treatment, the chlorination unit is used to provide a place for nitrogenation treatment, and the esterification unit is used to provide a place for esterification treatment.

[0043] The reaction unit, post-processing unit, diazotization unit, chlorination unit, and esterification unit are respectively provided with a feed port and a discharge port for conveying materials. The feed port of the reaction unit is used to convey the reaction raw materials, the discharge port of the reaction unit is connected with the feed port of the post-processing unit, the feed port of the post-processing unit is connected with the feed port of the diazotization unit, the discharge port of the diazotization unit is connected with the feed port of the chlorination unit, the discharge port of the chlorination unit is connected with the discharge port of the esterification unit, and the final product photosensitizer can be collected at the discharge port of the esterification unit. The above-mentioned connection mode can be connected through a pipeline.

[0044] In addition, the post-treatment unit is also provided with an acidifying agent inlet for conveying the acidifying agent; the diazotization unit is also provided with a sodium nitrite solution inlet for conveying the sodium nitrite solution; the chlorination unit is also provided with a chlorinating agent inlet for conveying the chlorinating agent; and the esterification unit is also provided with an esterifying agent inlet for conveying the esterifying agent.

[0045] The preparation method of the photosensitizer may specifically include the following steps: transporting the reaction raw materials into a reaction unit, performing an alkali melting treatment, and obtaining a first reactant; transporting the first reactant into a post-treatment unit, mixing it with an acidifier transported into the post-treatment unit through an acidifier inlet, performing an acidification treatment, and obtaining a mixed solution; and then performing solid-liquid separation on the mixed solution to obtain a first reaction liquid; transporting the first reaction liquid into a diazotization unit, mixing it with a sodium nitrite solution transported into the diazotization unit through a sodium nitrite solution inlet, performing a diazotization reaction, and then performing crystallization, filtering, and drying to obtain a diazotization product, and mixing the diazotization product with ethylene dichloride to obtain a second reaction liquid; the mass ratio of the diazotization product to ethylene dichloride is 1:(2-3); transporting the second reaction liquid into a chlorination unit, mixing it with a chlorinating agent transported into the chlorination unit through a chlorinating agent inlet, performing a chlorination treatment, and obtaining a third reaction liquid; transporting the third reaction liquid into an esterification unit, mixing it with an esterifying agent transported into the esterification unit through an esterifying agent inlet, performing an esterification treatment, and obtaining a photosensitizer.

[0046] Among them, 2-naphthylamine-1,5-disulfonic acid, solid base and catalyst enter the reaction unit through the feed port of the reaction unit, undergo alkali melting reaction, and obtain the first reactant; the first reactant is discharged through the discharge port of the reaction unit, enters the post-processing unit through the feed port of the post-processing unit, is mixed with the acidulant transported to the post-processing unit through the acidulant inlet, and undergoes acidification treatment to obtain a mixed solution; the mixed solution is then subjected to solid-liquid separation to obtain a first reaction liquid, at which point the first reaction liquid is substantially an acid solution containing 2-amino-1-naphthol-5-sulfonic acid.

[0047] In the high-temperature alkali melting treatment, the reaction materials are relatively viscous or even agglomerated, with poor fluidity, which is easy to cause, resulting in low reaction efficiency and yield of the traditional process. The present invention avoids the above problems by the synergistic effect of the continuous flow twin-screw reactor and the catalyst. This is because, on the one hand, under the pressurized high shear of the twin-screw reactor and the joint action of the catalyst, the fluidity and uniformity of the reaction materials are greatly enhanced, and local overheating and coking phenomena are avoided; on the other hand, the macromolecular ring structure of the catalyst makes the contact between the reaction raw materials sufficient, accelerates the reaction rate, and improves the reaction efficiency and yield. Among them, the catalyst is a crown ether, which is a macrocyclic polyether containing multiple -oxy-methylene-structural units in the molecule. Since the crown ether is a macromolecular cyclic compound, there is a large space inside it, so the catalyst can react with positive ions, especially alkali metal ions, and bring inorganic substances (such as solid bases) into organic substances (such as 2-naphthylamine-1,5-disulfonic acid), which can play a good phase transfer effect.

[0048] Furthermore, the reaction unit can adopt a twin-screw reactor to ensure that the material is heated evenly and reacts efficiently while achieving self-cleaning; the twin-screw reactor is mainly a device composed of two mutually meshing screws in an "8"-shaped barrel. The twin-screw reactor is a positive displacement conveying device, which forces the material to be pushed forward. On the other hand, the twin-screw reactor also produces a shearing effect on the material at the meshing point of the two screws.

[0049] Furthermore, the diazotization unit can use a microchannel reactor; a microreactor is a microchannel reactor, which is a micro reactor with a characteristic size between 10 and 300 microns (or 1000 microns) manufactured using precision machining technology. The "micro" in the microreactor means that the channel of the process fluid is at the micron level, rather than the small size of the micro reaction equipment or the small output of the product. The microreactor can contain millions or tens of millions of micro channels, so a very high output is also achieved. Due to its internal microstructure, the microreactor equipment has a very large specific surface area, which can reach hundreds or even thousands of times the specific surface area of ​​the stirred tank. The microreactor has excellent heat and mass transfer capabilities, which can achieve instantaneous uniform mixing of materials and efficient heat transfer, so many reactions that cannot be achieved in conventional reactors can be achieved in microreactors.

[0050] The first reaction liquid is discharged from the liquid phase discharge port of the post-treatment unit, enters the diazotization unit through the feed port of the diazotization unit, is mixed with the sodium nitrite solution transported to the diazotization unit through the sodium nitrite solution inlet, performs diazotization reaction, and then obtains a diazotization product after crystallization, filtration, and drying, and the diazotization product is mixed with dichloroethane to obtain a second reaction liquid; the mass ratio of the diazotization product to the dichloroethane is 1:(2-3), wherein the diazotization treatment is substantially a reaction between a 2-amino-1-naphthol-5-sulfonic acid solution and sodium nitrite, and the second reaction liquid is a solution containing at least 2-diazo-1-naphthoquinone-5-sulfonic acid.

[0051] The second reaction liquid is discharged from the discharge port of the diazotization unit, transported to the chlorination unit through the feed port of the nitridation unit, mixed with the chlorinating agent transported to the chlorination unit through the chlorinating agent inlet, and subjected to chlorination treatment to obtain a third reaction liquid. The nitridation treatment is essentially a reaction between 2-diazo-1-naphthoquinone-5-sulfonic acid and the chlorinating agent. The third reaction liquid is a solution containing 2-diazo-1-naphthoquinone-5-sulfonyl chloride.

[0052] The third reaction liquid is discharged from the discharge port of the nitridation unit, transported to the esterification unit through the feed port of the esterification unit, mixed with the esterification agent transported to the esterification unit through the esterification agent inlet, and subjected to esterification treatment to obtain a photosensitizer. The esterification reaction is essentially an esterification reaction between 2-diazo-1-naphthoquinone-5-sulfonyl chloride and the esterification agent.

[0053] According to the research of the present invention, the above-mentioned preparation method is used to prepare the photosensitive agent, which can realize continuous production, and the yield and quality of the prepared photosensitive agent are high. This is because, on the one hand, by using a continuous flow reaction device for preparation, by continuously inputting the reaction raw materials into the reaction device, the reaction products can be stably and continuously collected, thereby realizing continuous reaction and achieving the purpose of continuous production, greatly shortening the reaction time and greatly improving the reaction efficiency; on the other hand, by selecting specific catalysts, reaction raw materials and esterification agents, it is helpful to improve the yield and quality of the reaction products, and the preparation method is simple and easy to operate, which is conducive to large-scale production.

[0054] The present invention does not limit the selection of each raw material. For example, in some embodiments, the acidulant is a 30 wt % hydrochloric acid aqueous solution; the solid base includes at least one of potassium hydroxide and sodium hydroxide; and / or the chlorinating agent includes at least one of HSO3Cl, SOCl2, PCl3, and POCl3.

[0055] The present invention does not limit the amount of reaction raw materials added, and can be adjusted according to actual needs. For example, in some embodiments, the mass content of the catalyst in 2-naphthylamine-1,5-disulfonic acid is 0.5-2%, such as 0.5%, 1%, 1.5%, 2% or any two of them; and / or, the molar ratio of the solid base to 2-naphthylamine-1,5-disulfonic acid is (2-4): 1, such as 2: 1, 3: 1, 4: 1 or any two of them. The amount of reaction raw materials added can be controlled within the above range by controlling the feed rate.

[0056] By adjusting the feed rate of the reaction materials, it is helpful to further improve the yield and quality of the photosensitive agent. For example, in some embodiments, the feed rate of 2-naphthylamine-1,5-disulfonic acid and the catalyst is 10.1 to 40.4 g / min, such as 10.1 g / min, 20 g / min, 30 g / min, 40 g / min, 40.4 g / min or any two thereof; and / or, the feed rate of the solid base is 2.64 to 15.8 g / min, such as 2.64 g / min, 5 g / min, 10 g / min, 15 g / min, 15.8 g / min or any two thereof; and / or, the feed rate of the sodium nitrite solution is 9.37 to 56.2 g / min, such as 9.37 g / min. / min, 10g / min, 20g / min, 40g / min, 50g / min, 56.2g / min or a range consisting of any two thereof; and / or, the feed rate of the chlorinating agent is 3.23-12.92g / min, for example, 3.23g / min, 5g / min, 10g / min, 12.92g / min or a range consisting of any two thereof; and / or, the feed rate of the esterifying agent is 1.94-7.76g / min, for example, 1.94g / min, 2g / min, 4g / min, 6g / min, 7g / min, 7.76g / min or a range consisting of any two thereof.

[0057] The present invention does not limit the preparation parameters of the above preparation process, and can be adjusted according to the actual reaction situation. For example, in some embodiments, the temperature in the reaction unit is 200-300°C, that is, the temperature of the alkali melting treatment is 200-300°C; and / or, the temperature in the post-treatment unit is 10-30°C, that is, the temperature of the acidification and solid-liquid separation is 10-30°C; and / or, the temperature in the diazotization unit is 0-30°C, that is, the temperature of the diazotization treatment is 0-30°C; and / or, the temperature in the chlorination unit is 50-80°C, that is, the temperature of the chlorination treatment is 50-80°C; and / or, the temperature in the esterification unit is 30-60°C, that is, the temperature of the esterification treatment is 50-80°C.

[0058] In some embodiments, the molar ratio of the sodium nitrite solution to the 2-amino-1-naphthol-5-sulfonic acid in the first reaction solution is (1-1.2):1; and / or the mass concentration of the sodium nitrite solution is 10-30%; the molar ratio of the chlorinating agent to the 2-diazo-1-naphthoquinone-5-sulfonic acid in the second reaction solution is (1-1.2):1; and / or the molar ratio of the 2-diazo-1-naphthoquinone-5-sulfonyl chloride and the esterifying agent in the third reaction solution is (3-4):1.

[0059] In the present invention, the reaction unit, post-treatment unit, diazotization unit, chlorination unit, and esterification unit each independently include at least one reactor, wherein the material channel in the reactor is made of single crystal silicon, special glass, ceramic, stainless steel coated with corrosion-resistant coating, metal alloy, polytetrafluoroethylene, etc.

[0060] Furthermore, the reaction unit can use a twin-screw reactor to ensure that the material is heated evenly and reacts efficiently while achieving self-cleaning; the diazotization unit can use a microchannel reactor; and the chlorination unit and the esterification unit can use a reaction kettle.

[0061] The preparation method of the photosensitive agent provided by the present invention has a safe and efficient production process, a high product yield, greatly reduces the production cost, improves the safety of product production, and realizes the high-efficiency, high-quality, and large-scale production of the photosensitive agent; the preparation method of the present invention has no amplification effect, which greatly reduces the difficulty of industrial application. When it is amplified to industrialization, it does not need to go through tedious and complicated multiple step-by-step amplifications and adjustment and optimization of process conditions and parameters, and can be amplified to the required production scale at one time, which greatly saves manpower, material resources and project development time; in addition, the safety of the preparation method of the present invention is greatly improved, and the continuous flow reaction device has a relatively small liquid holding capacity and excellent heat transfer characteristics, and the short reaction time makes the process safer. The reaction time of the present invention is greatly shortened, and the reaction efficiency is greatly improved; the flow rate of the reaction material in the reaction device of the present invention is stable, the production process is stable, and thus the product quality is stable and the reproducibility is good; and the reaction device is small in size and occupies a small area, which greatly saves plant land.

[0062] In addition, the preparation method provided by the present invention can achieve a photosensitive agent yield of ≥60%, and the content of tris (6-diazo-5-oxo-5,6-dihydro-1-naphthalenesulfonic acid)-4-benzoyl-1,2,3-benzenetriol (phenol) ester (PAC) in the photosensitive agent is ≥90%; wherein the chemical formula of tris (6-diazo-5-oxo-5,6-dihydro-1-naphthalenesulfonic acid)-4-benzoyl-1,2,3-benzenetriol (phenol) ester (PAC) is as shown in Formula 1:

[0063]

[0064] The present invention will be further described below by means of specific examples and comparative examples.

[0065] like Figure 1 The figure shows a schematic diagram of the continuous flow reaction device of the present invention, which includes a reaction unit, a post-treatment unit, a diazotization unit, a chlorination unit, and an esterification unit connected in sequence;

[0066] The feed port of the reaction unit is used to transport the reaction raw materials, the discharge port of the reaction unit is connected to the feed port of the post-treatment unit, the feed port of the post-treatment unit is connected to the feed port of the diazotization unit, the discharge port of the diazotization unit is connected to the feed port of the chlorination unit, the discharge port of the chlorination unit is connected to the discharge port of the esterification unit, and the final product is collected at the discharge port of the esterification unit;

[0067] The post-treatment unit is also provided with an acidifying agent inlet for conveying the acidifying agent; the diazotization unit is also provided with a sodium nitrite solution inlet for conveying the sodium nitrite solution; the chlorination unit is also provided with a chlorinating agent inlet for conveying the chlorinating agent; the esterification unit is also provided with an esterifying agent inlet for conveying the esterifying agent;

[0068] In the following examples, raw material 1 (2-naphthylamine-1,5-disulfonic acid and catalyst), raw material 2 (solid base), raw material 3 (sodium nitrite solution), raw material 4 (chlorinating agent) and raw material 5 (esterifying agent) are successively transported to a continuous flow reaction device by a constant flow pump. The feed rates are shown in Table 1, wherein feed rate 1 represents the feed rate of raw material 1, feed rate 2 represents the feed rate of raw material 2, feed rate 3 represents the feed rate of raw material 3, feed rate 4 represents the feed rate of raw material 4, feed rate 5 represents the feed rate of raw material 5, temperature zone 1 represents the temperature in the reaction unit, temperature zone 2 represents the temperature in the post-treatment unit; temperature zone 3 represents the temperature in the diazotization unit, temperature zone 4 represents the temperature in the chlorination unit, and temperature zone 5 represents the temperature in the esterification unit.

[0069] The various process parameters of each specific embodiment are shown in Table 1.

[0070] Example 1

[0071] The preparation method of the photosensitizer of this embodiment may specifically include the following steps:

[0072] The reaction raw materials are transported into the reaction unit and subjected to alkaline melting treatment to obtain a first reactant; wherein the reaction raw materials include 2-naphthylamine-1,5-disulfonic acid, KOH and dicyclohexane-18-crown-6, and the amount of dicyclohexane-18-crown-6 added is 1% of the mass of 2-naphthylamine-1,5-disulfonic acid;

[0073] The first reactant is transported to a post-processing unit, mixed with an acidifier transported to the post-processing unit through an acidifier inlet, and subjected to an acidification treatment to obtain a mixed solution; wherein the acidifier is hydrochloric acid; and then the mixed solution is subjected to solid-liquid separation to obtain a first reaction solution;

[0074] The first reaction liquid is transported to the diazotization unit, mixed with the sodium nitrite solution transported to the diazotization unit through the sodium nitrite solution inlet, and subjected to diazotization reaction, and then crystallized, filtered, and dried to obtain a diazotization product, and the diazotization product is mixed with dichloroethane to obtain a second reaction liquid; the mass ratio of the diazotization product to the dichloroethane is 1:2; the mass concentration of the sodium nitrite solution is 10%;

[0075] The second reaction liquid is transported to the chlorination unit, mixed with the chlorinating agent transported to the chlorination unit through the chlorinating agent inlet, and chlorinated to obtain a third reaction liquid; wherein the chlorinating agent is HSO3Cl;

[0076] The third reaction liquid is transported to the esterification unit, mixed with the esterification agent transported to the esterification unit through the esterification agent inlet, and subjected to esterification treatment to obtain a photosensitizer; wherein the esterification agent is 4HBP.

[0077] Embodiments 2 to 11

[0078] The preparation process is basically the same as that of Example 1, except that the specific type of raw materials, feed rate, and reaction temperature are different, as shown in Table 1.

[0079] Comparative Example 1

[0080] The preparation process is basically the same as that of Example 1, except that no catalyst is added, and the specific type of raw materials, feed rate, and reaction temperature are different, as shown in Table 2.

[0081] The reaction products discharged from the discharge port of the esterification unit in the above-mentioned embodiments and comparative examples, i.e., photosensitizers, were collected and the PAC content was detected by HPLC. Figure 2 , Figure 3 and Table 1.

[0082] The yield was calculated according to total yield = (product mass of photosensitizer / product molecular weight) / (mass of 2-naphthylamine-1,5-disulfonic acid / molecular weight of 2-naphthylamine-1,5-disulfonic acid).

[0083] Table 1

[0084] Retention time / min type Peak width min Peak area Peak height Peak area% 2.132 VV 0.61 1071.82 203.45 99.04 3.254 MM 0.16 1043 2.07 0.96

[0085] Table 2

[0086]

[0087] according to Figure 2 It can be seen that when the final product of Example 2 is tested by HPLC, from left to right, the first peak is PAC, and the second peak is other impurities. According to the peak area, it can be calculated that the PAC content in the final product is about 99%.

[0088] The continuous flow preparation method of the photosensitizer provided by the present invention is carried out by using a continuous flow reaction device and limiting the specific type of the catalyst, which is beneficial to improving the yield and quality of the photosensitizer. The preparation method is simple and easy to operate, which is beneficial to realizing large-scale production.

[0089] The preferred specific embodiments and experimental verification of the present invention are described in detail above. It should be understood that ordinary technicians in this field can make many modifications and changes based on the concept of the present invention without creative work. Therefore, all technical solutions that can be obtained by technicians in this technical field based on the concept of the present invention through logical analysis, reasoning or limited experiments on the basis of the prior art should be within the scope of protection determined by the claims.

Claims

1. A continuous flow preparation method for a photosensitizer, characterized in that: The photosensitizer is prepared by using a continuous flow reaction device, wherein the continuous flow reaction device comprises a reaction unit, a post-treatment unit, a diazotization unit, a chlorination unit, and an esterification unit connected in sequence; The continuous flow preparation method of the photosensitizer comprises the following steps: The reaction raw materials are transported to the continuous flow reaction device through the feed port, and flow through the reaction unit and the post-treatment unit in sequence to obtain a first reaction liquid; The first reaction liquid flows through the diazotization unit, the chlorination unit, and the esterification unit in sequence through the feed port, and reacts with the sodium nitrite solution, the chlorination agent, and the esterification agent transported to the diazotization unit, the chlorination unit, and the esterification unit in sequence to obtain a photosensitizer; The reaction raw materials include 2-naphthylamine-1,5-disulfonic acid, a solid base and a catalyst, the catalyst includes at least one of 1,4,7,10,13,16-hexaoxacyclooctadecane, 1,4,7,10,13-pentacyclopentadecane and dicyclohexane-18-crown-6, and the esterification agent includes at least one of 2,3,4-trihydroxybenzophenone and 2,3,4,4-tetrahydroxybenzophenone.

2. The preparation method according to claim 1, characterized in that: The first reaction liquid is transported to a diazotization unit, mixed with a sodium nitrite solution transported to the diazotization unit through a sodium nitrite solution inlet, and subjected to a diazotization reaction. After crystallization, filtration, and drying, a diazotization product is obtained. The diazotization product is mixed with ethylene dichloride to obtain a second reaction liquid; the mass ratio of the diazotization product to the ethylene dichloride is 1:(2-3); The second reaction liquid is transported to a chlorination unit, mixed with a chlorinating agent transported to the chlorination unit through a chlorinating agent inlet, and subjected to chlorination treatment to obtain a third reaction liquid; The third reaction liquid is transported to the esterification unit, mixed with the esterification agent transported to the esterification unit through the esterification agent inlet, and subjected to esterification treatment to obtain a photosensitizer; Wherein, the molar ratio of the chlorinating agent to the 2-diazo-1-naphthoquinone-5-sulfonic acid in the second reaction solution is (1-1.2):1; The molar ratio of 2-diazo-1-naphthoquinone-5-sulfonyl chloride to the esterifying agent in the third reaction solution is (3-4):

1.

3. The preparation method according to claim 1, characterized in that: The solid alkali comprises at least one of potassium hydroxide and sodium hydroxide; and / or, The chlorinating agent includes at least one of HSO3Cl, SOCl2, PCl3, and POCl3.

4. The preparation method according to claim 1, characterized in that: The mass content of the catalyst in the 2-naphthylamine-1,5-disulfonic acid is 0.5-2%; and / or, The molar ratio of the solid base to the 2-naphthylamine-1,5-disulfonic acid is (2-4):

1.

5. The preparation method according to claim 1, characterized in that: The feed rate of the 2-naphthylamine-1,5-disulfonic acid and the catalyst is 10.1 to 40.4 g / min; and / or, The solid alkali feed rate is 2.64-15.8 g / min; and / or, The feeding rate of the sodium nitrite solution is 9.37-56.2 g / min; and / or, The feeding rate of the chlorinating agent is 3.23-12.92 g / min; and / or, The feed rate of the esterification agent is 1.94-7.76 g / min.

6. The preparation method according to claim 1, characterized in that: The temperature in the reaction unit is 200-300° C.; and / or, The temperature in the post-processing unit is 10-30° C.; and / or, The temperature in the diazotization unit is 0 to 30° C.; and / or, The temperature in the chlorination unit is 50-80° C.; and / or, The temperature in the esterification unit is 30-60°C.

7. The preparation method according to claim 1, characterized in that: The molar ratio of the sodium nitrite solution to the 2-amino-1-naphthol-5-sulfonic acid in the first reaction solution is (1-1.2):1; and / or, The mass concentration of the sodium nitrite solution is 10-30%.

8. The preparation method according to claim 1, characterized in that: The reaction unit, post-treatment unit, diazotization unit, chlorination unit and esterification unit each independently include at least one reactor.

9. The preparation method according to any one of claims 1 to 8, characterized in that: The yield of tris(6-diazo-5-oxo-5,6-dihydro-1-naphthalenesulfonic acid)-4-benzoyl-1,2,3-benzenetriol) ester in the photosensitizer is ≥60%.

10. The preparation method according to any one of claims 1 to 8, characterized in that: The content of tris(6-diazo-5-oxo-5,6-dihydro-1-naphthalenesulfonic acid)-4-benzoyl-1,2,3-benzenetriol) in the photosensitizer is ≥90%; The chemical formula of the tris(6-diazo-5-oxo-5,6-dihydro-1-naphthalenesulfonic acid)-4-benzoyl-1,2,3-benzenetriol ester is shown in Formula 1:

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