Flexible co-production manufacturing technology of photoinitiators APi-307 and Irgacure 907
Patent Information
- Application Number
- CN202411139212.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-08-20
- Publication Date
- 2026-03-03
Smart Images
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Abstract
Description
[Technical Field]
[0001] This invention relates to the field of photocurable new material chemicals, and in particular to the flexible manufacturing technology of Shenzhen Youwei Technology Co., Ltd.’s self-developed photoinitiator APi-307 and commercially available Irgacure 907. It can flexibly switch between the production of one of the two or the combined production of both on shared production equipment and basic process sections. The production line and process mutually empower each other to reduce costs and increase efficiency, and achieve outstanding operational convenience and excellent low-cost competitiveness. [Background Technology]
[0002] In the field of photocurable new materials technology, photoinitiators are key materials that absorb the energy of radiation sources and / or electron beams to generate active free radicals or cationic acids, thereby inducing the chemical polymerization of radiation-resistant systems containing olefin bonds. Therefore, there is a continuous demand for technological innovation in the industry, namely, to continuously improve the manufacturing process technology of photoinitiators in order to gain cost competitiveness and environmental advantages.
[0003] As shown in the structure below, the novel amino ketone photoinitiator APi-307, developed and industrialized by our company (Shenzhen Youwei Technology Holding Group Co., Ltd.), is facing increasing user demand due to its excellent performance, including but not limited to high initiation activity, sulfur-free, low cost, odorless, yellowing resistance, and reproductive and developmental safety. It is increasingly being used as a highly efficient alternative to the traditional photoinitiator Irgacure 907, especially in the fields of UV-curable inks, adhesives, and coatings.
[0004]
[0005] The preparation of APi-307 begins with the so-called Friedel-Crafts acylation reaction of biphenyl and isobutyryl chloride. Similarly, as is well known to those skilled in the art, the preparation of Irgacure 907 begins with the Friedel-Crafts acylation reaction of chlorobenzene and isobutyryl chloride. Therefore, although the production processes for APi-307 and Irgacure 907 are similar, when a production unit switches from Irgacure 907 to APi-307, a shutdown for cleaning and overhaul of the entire reactor system is unavoidable to prevent contamination. This is undesirable in production practice because such cleaning not only causes shutdowns and reduces plant efficiency but also generates additional waste and presents environmental treatment challenges.
[0006] Through practical exploration, we have discovered that, surprisingly, APi-307 and Irgacure 907 can be manufactured in a way that allows for seamless switching of production equipment without shutdown and / or maintenance, thanks to the precise control of process conditions. This enables highly flexible single-unit or multi-unit production, further enhancing their low-cost economic competitiveness and broad application adaptability. [Summary of the Invention]
[0007] This application has now discovered that, as shown in the following reaction formula (I), biphenyl and isobutyryl chloride undergo a Friedel-Crafts acylation reaction under suitable reaction conditions to give biphenyl isobutyrone A; ketone A and halogen [X] undergo a halogenation reaction under reaction conditions to give haloketone B; subsequently, B undergoes an amination reaction with morpholine to give the product APi-307.
[0008] Under appropriate reaction conditions, although chlorobenzene is a so-called electrophilic substituted active aromatic hydrocarbon well known to those skilled in the art, no competitive Friedel-Crafts acylation reaction (against biphenyl) of chlorobenzene was observed, even when using a large excess of chlorobenzene as a solvent. Therefore, there is no need to worry about contamination caused by any chlorobenzene acylation reaction when switching directly from Irgacure 907 production to APi-307 production on the same production unit (i.e., without stopping the unit system for cleaning).
[0009]
[0010] [X] is a halogen, Cl or Br; preferably chlorine; conditions are at least one of solvent, temperature, pressure (or vacuum), or additive.
[0011] The solvent is selected from at least one of substituted or unsubstituted aromatic hydrocarbons, straight-chain or branched aliphatic hydrocarbons, (sulfoxides), amides, ethers, alcohols, esters, ketones, nitriles, carboxylic acids, water, amines, carbonates, ionic liquids, and supercritical carbon dioxide containing 1-24 carbon atoms; or the liquid or molten substrate itself acts as the solvent medium. Chlorinated hydrocarbons are preferred solvents, and chlorobenzene is a more preferred solvent.
[0012] The use of solvents is preferred but not necessary. Under certain conditions, solvents may not be used, that is, the solution or melt of the reactants may be used, or the reactants may be directly mixed and then reacted under heating and grinding conditions. These advantages are well known to professionals in this field.
[0013] The temperature is -25 to 450 degrees Celsius, preferably -20 to 300 degrees Celsius; more preferably -20 to 200 degrees Celsius.
[0014] Pressure refers to the pressure under which the reaction system is carried out, or under a certain degree of vacuum. The pressure of the reaction process is 0.01-100 atmospheres, preferably 0.1-10 atmospheres, and even more preferably atmospheric pressure.
[0015] Additives are reaction catalysts or accelerators, and there are no particular limitations.
[0016] In the step of converting biphenyl to ketone A, the preferred reaction temperature is -25 to 120 degrees Celsius;
[0017] In the step of converting ketone A to haloketone B, melt A is preferably used as the reaction medium.
[0018] In the step of converting haloketone B to APi-307, excess morpholine is preferably used as the reaction medium.
[0019] This application further discovers that, as shown in reaction formula (II) below, under suitable reaction conditions, biphenyl and excess chlorobenzene (i.e., chlorobenzene serves as both a substrate and a reaction medium) undergo a Friedel-Crafts acylation reaction with isobutyryl chloride simultaneously to co-produce ketones A and C; without separation, the mixture and halogen [X] undergo a halogenation reaction under the reaction conditions to yield haloketones B and D; subsequently, a mixture of B and D undergoes amination reaction directly with morpholine to co-produce the APi-307 product and the precursor 907-Cl of Irgacure 907.
[0020] As is well known to industry professionals, 907-Cl, after separation, can directly react with sodium methimazole to yield Irgacure 907. This fully flexible, shared co-production process offers significant cost reduction and efficiency improvement.
[0021]
[0022] In the conversion steps from biphenyl and chlorobenzene to the mixture of ketones A and C, the preferred reaction temperature is 20-200 degrees Celsius; that is, the reaction does not require selectivity, and therefore the temperature is higher than that of the acylation process in general formula (I).
[0023] In the conversion step from ketone mixtures A and C to haloketone mixtures B and D, it is preferable to use the melts of A and C as the reaction medium;
[0024] In the step of converting the haloketone mixtures B and D into APi-307 and 907-Cl, excess morpholine is preferably used as the reaction medium.
[0025] The technology disclosed in this invention is the first to achieve flexible switching or co-production of APi-307 and Irgacure 907 on the same production unit in a safe and efficient manner without stopping or cleaning, resulting in extremely rare cost reduction and efficiency improvement benefits in the production and manufacturing practice of photoinitiators.
[0026] The essence of the invention will be further illustrated in the embodiments.
Detailed Implementation Methods
[0027] Example 1:
[0028] In a 3-liter four-necked flask, 200 g of biphenyl and 960 g of chlorobenzene were added sequentially (the system was protected from moisture by nitrogen, the same below). The reaction flask was placed in a 0°C cold bath, and 230 g of anhydrous aluminum trichloride was slowly added and stirred until homogeneous. 158 g of isobutyryl chloride was slowly added dropwise to the reaction flask in portions. The reaction was exothermic, and the temperature of the reaction solution needed to be controlled to keep the temperature below 3°C. After the isobutyryl chloride was added, the reaction was continued at a low temperature for 0.5 hours until the reaction was complete. 0.3 mL of the reaction solution was added to 1 mL of chlorobenzene, mixed well, and quenched with water. The organic phase was removed by adding sodium sulfate, dried, and quantitatively analyzed by GC using the internal standard method. The yield of biphenyl isobutyl ketone A was 99.5%, and chlorophenyl isobutyl ketone C was not detected. The reaction mixture was quenched and the chlorobenzene was recovered by vacuum distillation. The crude product was added to 0.3 L of n-hexane, heated to dissolve, and then stirred at a low temperature to crystallize, yielding 314 g of white needle-like product.
[0029] The above procedure was repeated, but the reaction was maintained at room temperature, yielding 316 g of biphenyl isobutyl ketone A, with no detection of chlorophenyl isobutyl ketone C. The above experiments demonstrate that using chlorobenzene as a solvent for the biphenyl acylation reaction is entirely feasible under appropriate reaction temperature conditions, without being affected by impurities in the acylation reaction.
[0030] Example 2:
[0031] 25 g of biphenyl isobutyl ketone B was added to a 100 mL three-necked flask and heated to melt. Chlorine gas was introduced at a rate of approximately 0.5 L / min within a temperature range of 65-100 °C. After about 45 minutes, the reaction solution solidified. The system was then heated to 100 °C to melt the reaction solution, and chlorine was continued to be introduced for 20 minutes. A sample was taken and dissolved in dichloroethane. Gas chromatography (GC) analysis showed that the raw material was almost completely converted, and the yield of biphenyl chloroisobutyl ketone B was 96.7%.
[0032] This experiment demonstrates that the chlorination reaction can proceed efficiently and cleanly to produce the target product, chloroketone, without the need for solvents or catalysts.
[0033] Example 3:
[0034] In a 1-liter three-necked flask, 450 ml of xylene, 27.4 g of chlorobiphenyl isobutyl ketone B, and 20 g of morpholine were mixed. 2.4 g of anhydrous aluminum trichloride was slowly added while stirring. The mixture was stirred and reacted overnight at 100 °C. After quenching, the organic phase was washed with water to separate the mixture, dried, filtered, and concentrated to obtain 32 g of APi-307 pale yellow product.
[0035] Example 4:
[0036] In a 3-liter four-necked flask, 230 g of biphenyl and 750 g of chlorobenzene were added sequentially. While stirring, 515 g of anhydrous aluminum trichloride was slowly added to the mixture. 355 g of isobutyryl chloride was added dropwise in portions to the reaction flask. The reaction was exothermic, and the temperature was raised, controlling the dropping rate to maintain the reaction solution temperature at 60-90°C. After the reaction was complete, 0.5 mL of the reaction solution was added to 1 mL of chlorobenzene, mixed thoroughly, and quenched with water. The organic phase was then treated with sodium sulfate to remove water, dried, and quantitatively analyzed by GC using the internal standard method. The yield of biphenyl isobutyl ketone A was 99.5%, and the yield of chlorophenyl isobutyl ketone C was 98.4%. After quenching the reaction mixture, excess chlorobenzene was recovered by vacuum distillation, yielding 603 g of mixed ketone product.
[0037] This experiment shows that when the acylation reaction is carried out at a higher temperature, even with a reduction in the amount of chlorobenzene used as the solvent medium, both biphenyl and chlorobenzene can be efficiently converted into the corresponding ketones; and both can be used directly in the next chlorination reaction without separation and purification.
[0038] Example 5:
[0039] Following the procedure in Example 2, 603 grams of a mixture of ketones A and C were directly heated and melted, with chlorine gas continuously introduced at a rate of approximately 0.5 L / min within a temperature range of 60-80°C. After the reaction was complete, a sample was taken and dissolved in dichloroethane. Gas chromatography (GC) confirmed that the raw materials had been completely converted, yielding a mixture of 680 grams of chloroketones B and D.
[0040] Example 6:
[0041] Following the procedure in Example 3, 450 mL of xylene and a mixture of 36.4 g of isobutyl chloroketone B and D, along with 28 g of morpholine, were mixed in a 1 L three-necked flask. 3.2 g of anhydrous aluminum trichloride was slowly added with stirring. The mixture was stirred overnight at 100 °C. After quenching, the organic phase was washed with water, dried, and filtered. The concentrate was then dissolved in methanol and decolorized with activated carbon. After filtration and concentration, 42.6 g of APi-307 and 907-Cl pale yellow product were obtained.
[0042] It should be emphasized that the above embodiments are merely exemplary and not limiting. Based on the disclosure of this application, any adjustments or changes to the reaction conditions or parameters that a person skilled in the art might normally adopt will not deviate from the spirit of the invention. The scope of protection of this patent shall be determined by the relevant claims.
Claims
1. A production process for the photoinitiator APi-307. As shown in reaction formula (I), the process is characterized by using chlorobenzene as a solvent, biphenyl and isobutyryl chloride undergoing a Friedel-Crafts acylation reaction under suitable reaction conditions to obtain biphenyl isobutyl ketone A; ketone A and halogen [X] undergo a halogenation reaction under suitable reaction conditions to obtain haloketone B; subsequently, B undergoes an amination reaction with morpholine to obtain the APi-307 product. Wherein [X] is a halogen, Cl or Br; preferably chlorine; and conditions are at least one of solvent, temperature, pressure (or vacuum), or additive.
2. A co-production process for photoinitiator APi-307 and Irgacure 907. As shown in reaction formula (II), under suitable reaction conditions, biphenyl and chlorobenzene undergo a Friedel-Crafts acylation reaction with isobutyryl chloride simultaneously to co-produce ketones A and C; without separation, the mixture and halogen [X] undergo a halogenation reaction under the reaction conditions to give haloketones B and D; subsequently, the mixture of B and D, without separation, undergoes amination reaction with morpholine to co-produce the APi-307 product and the Irgacure 907 precursor 907-Cl:
3. According to claims 1 and 2, the solvent is selected from at least one of substituted or unsubstituted aromatic hydrocarbons containing 1-24 carbon atoms, straight-chain or branched aliphatic hydrocarbons, (sulfoxide) sulfones, amides, ethers, alcohols, esters, ketones, nitriles, carboxylic acids, water, amines, carbonates, ionic liquids, and supercritical carbon dioxide; or the liquid or molten substrate itself acts as the solvent medium. A preferred solvent is a chlorinated hydrocarbon, and a more preferred solvent is chlorobenzene. The temperature is -25 to 450 degrees Celsius, preferably -20 to 300 degrees Celsius; more preferably -20 to 200 degrees Celsius. The pressure refers to the reaction system being carried out under pressure or a certain vacuum condition; the reaction pressure is 0.01 to 100 atmospheres, preferably 0.1 to 10 atmospheres, and more preferably atmospheric pressure. The additive is a reaction catalyst or promoter.
4. According to claim 1, in the step of converting biphenyl to ketone A, the preferred reaction temperature is -25 to 120 degrees Celsius; in the step of converting ketone A to haloketone B, melt A is preferably used as the reaction medium; in the step of converting haloketone B to APi-307, excess morpholine is preferably used as the reaction medium.
5. According to claim 2, in the step of converting biphenyl and chlorobenzene into mixtures of ketones A and C, the preferred reaction temperature is 20-200 degrees Celsius; in the step of converting mixtures of ketones A and C into mixtures of haloketones B and D, the melt of A and C is preferably used as the reaction medium; in the step of converting mixtures of haloketones B and D into APi-307 and 907-Cl, excess morpholine is preferably used as the reaction medium.
6. Use of APi-307 and / or Irgacure 907 manufactured according to claims 1-5 as photopolymerization initiators for olefin-containing unsaturated systems.