Polymerization inhibitor ZJ5575 and preparation method thereof

Abstract

The invention relates to the technical field of polymerization inhibitors, and particularly discloses a polymerization inhibitor ZJ5575 and a preparation method thereof. A preparation method of a polymerization inhibitor ZJ5575 comprises the following steps: mixing phosphite ester, a polymerization inhibitor 701 and a catalyst, carrying out a reaction at 115-125 DEG C for 10-12 h, then adding toluene and water, carrying out stirring at 35-45 DEG C for 2-2.5 h, carrying out standing layering to obtain an upper organic phase, then adding water into the organic phase again, carrying out negative pressure distillation at 55-65 DEG C, and carrying out filtration, washing and drying to obtain the polymerization inhibitor ZJ5575. And cooling to 22-28 DEG C after the toluene is completely removed, centrifuging to obtain a solid, and drying to obtain the polymerization inhibitor ZJ5575, the phosphite being one of triethyl phosphite or trimethyl phosphite. According to the preparation method disclosed by the invention, the yield of the product polymerization inhibitor ZJ5575 can be increased to 98.58%, and meanwhile, the discharge amount of wastewater is remarkably reduced.

Description

Technical Field

[0001] The present application relates to the technical field of polymerization inhibitors, and in particular to a polymerization inhibitor ZJ5575 and a preparation method thereof. Background Art

[0002] Inhibitor is an industrial additive, usually used to prevent the progress of polymerization. When the inhibitor is put into the system of the material to be inhibited according to a certain amount of polymerization inhibition, the polymerization inhibition effect can be achieved. The inhibitor molecules react with chain free radicals to form non-free radical substances or low-activity free radicals that cannot be triggered, thereby terminating the polymerization. In the actual use of polymerization inhibitors, the selection of polymerization inhibitors mainly requires that the selected polymerization inhibitors have a high polymerization inhibition efficiency, and its solubility in the monomer and its compatibility with the monomer should also be considered, and the polymerization inhibitor should be easily removed from the monomer by distillation or chemical methods. At the same time, the polymerization inhibitor must also have multiple characteristics such as non-toxic, harmless, environmentally friendly, stable polymerization inhibition performance, low price and easy availability.

[0003] Inhibitors are mainly used as stabilizers and inhibitors for polymer materials. Their main function is to inhibit the oxidation and decomposition reactions of polymers during processing, storage and use, thereby extending the service life of polymers. They are widely used in polymer industries such as plastics, rubber, and fibers, such as in the production of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and photocurable reactive diluent multifunctional acrylate.

[0004] In the prior art, in order to prepare the polymerization inhibitor, a variety of raw materials are usually used to carry out chemical reactions under specific conditions. For example, a common method is to react phosphorus trichloride with a nitroxide free radical compound under the action of a catalyst, and then obtain the target product through a series of separation and purification steps. In addition, there are also methods of synthesizing through multi-step reactions and methods of reacting in a specific solvent system. These methods meet the needs of industrial production to a certain extent, but there are still certain technical problems in the actual application process.

[0005] The preparation process of polymerization inhibitors usually produces a large amount of wastewater, which brings great pressure to environmental protection. At the same time, the existing preparation methods are often complicated, difficult to operate, and have certain technical requirements for production equipment and operators. These problems not only increase production costs, but also limit the large-scale application of polymerization inhibitors. Therefore, the development of a simple and efficient preparation method has become a technical problem that needs to be solved urgently. Summary of the invention

[0006] In order to solve the above technical problems, the present application provides an inhibitor ZJ5575 and a preparation method thereof.

[0007] In the first aspect, the present application provides a method for preparing an inhibitor ZJ5575, comprising the following steps: mixing a phosphite, an inhibitor 701 and a catalyst, reacting at a temperature of 115-125°C for 10-12h, then adding toluene and water, stirring at a temperature of 35-45°C for 2-2.5h, standing to separate into layers, obtaining an upper organic phase, then adding water to the organic phase again, performing negative pressure distillation at a temperature of 55-65°C, cooling to 22-28°C after the toluene is completely removed, centrifuging to obtain a solid, and drying to obtain an inhibitor ZJ5575, wherein the phosphite is one of triethyl phosphite or trimethyl phosphite.

[0008] Preferably, the phosphite is triethyl phosphite.

[0009] By adopting the above technical scheme, the present application adopts a method of thermally reacting phosphite with inhibitor 701 under the action of a catalyst, which promotes the ester exchange reaction of phosphite and the free radical reaction of inhibitor 701, thereby forming a precursor of inhibitor ZJ5575, and then adding toluene and water for extraction, and utilizing the difference in solubility of the components in the two phases to achieve effective separation, and the organic phase is distilled to remove the solvent by negative pressure, and the product is further purified. Finally, high-purity inhibitor ZJ5575 is obtained by centrifugation and drying. This method simplifies the operation process, significantly reduces the generation of wastewater, reduces the pressure on environmental protection in the process of preparing inhibitor ZJ5575, and effectively promotes the large-scale production and application of inhibitor ZJ5575.

[0010] Furthermore, the present application ultimately utilizes triethyl phosphite as a raw material, combined with specific reaction conditions and process flow, which helps to further improve the yield of the product while significantly reducing wastewater discharge, with the final total output wastewater volume as low as 2200 mL.

[0011] Preferably, the molar ratio of the phosphite to the inhibitor 701 is 1:(2.8-3.3).

[0012] Preferably, the molar ratio of the phosphite to the inhibitor 701 is 1:(2.9-3.2).

[0013] Preferably, the molar ratio of the phosphite to the inhibitor 701 is 1:3.

[0014] By adopting the above technical scheme, the present application gradually controls the molar ratio of phosphite and inhibitor 701, optimizes the reaction conditions, significantly improves the purity of the product, reduces the generation of by-products, simplifies the subsequent treatment process, and thereby effectively reduces the amount of wastewater discharged. Experimental data show that when the present application controls the molar ratio of phosphite and inhibitor 701 at 1:3, the purity of inhibitor ZJ5575 is as high as 98.58%, and the total output wastewater volume after all the inhibitor 701 is consumed is as low as 2200 mL.

[0015] Preferably, the catalyst includes any one of tetraisopropyl titanate, tetraethyl titanate and tetrabutyl titanate.

[0016] Preferably, the catalyst is tetraisopropyl titanate.

[0017] By adopting the above technical scheme, the present application utilizes tetraisopropyl titanate as a catalyst, which can further improve the consistency of catalytic efficiency and the stability of product quality compared to tetraethyl titanate and tetrabutyl titanate, and further promotes the effective contact between phosphite and inhibitor 701, improves the selectivity of the two reactions, reduces by-products, and improves the purity of the final product. In addition, tetraisopropyl titanate is easier to separate and remove from the final product, simplifies the subsequent treatment process and reduces production costs, and the waste water generated during the use of tetraisopropyl titanate is less, which helps environmental protection and meets the principles of green chemistry. Therefore, the catalyst used in the present invention not only improves the reaction rate and yield, but also takes into account economic benefits and environmental benefits.

[0018] In a second aspect, the present application provides an inhibitor ZJ5575 prepared by the above preparation method.

[0019] In summary, this application has the following beneficial technical effects: 1. The present application adopts a method of thermally reacting phosphite with inhibitor 701 under the action of a catalyst, which promotes the ester exchange reaction of phosphite and the free radical reaction of inhibitor 701, thereby forming a precursor of inhibitor ZJ5575, and then adds toluene and water for extraction, and uses the difference in solubility of the components in the two phases to achieve effective separation, and removes the solvent from the organic phase by negative pressure distillation to further purify the product. Finally, high-purity inhibitor ZJ5575 is obtained by centrifugation and drying, and its purity can reach up to 98.58%. This method simplifies the operation process and significantly reduces the generation of wastewater; and the present application finally uses triethyl phosphite as a raw material, combined with specific reaction conditions and process flow, which helps to further improve the stability and yield of the product, while reducing the wastewater discharge to 2500mL; 2. The present application gradually controls the molar ratio of phosphite and inhibitor 701, optimizes the reaction conditions, significantly improves the purity of the product, reduces the generation of by-products, simplifies the subsequent treatment process, and thereby effectively reduces the amount of wastewater discharged; 3. The present application utilizes tetraisopropyl titanate as a catalyst, further improving the consistency of catalytic efficiency and the stability of product quality, and further promoting the effective contact between phosphite and inhibitor 701, improving the selectivity of the two reactions, reducing by-products, and improving the purity of the final product. In addition, tetraisopropyl titanate is easier to separate and remove from the final product, simplifies the subsequent treatment process and reduces production costs, and the waste water generated during the use of tetraisopropyl titanate is less, which helps environmental protection and meets the principles of green chemistry. Therefore, the catalyst used in the present invention not only improves the reaction rate and yield, but also takes into account economic benefits and environmental benefits. DETAILED DESCRIPTION

[0020] Material Source Unless otherwise specified, the raw materials used in this application are all commercially available products, specifically: Triethyl phosphite was purchased from Shandong Taixi Chemical Co., Ltd., CAS No. 122-52-1; Trimethyl phosphite was purchased from Shandong Qiyun Chemical Technology Co., Ltd., CAS No. 121-45-9; Inhibitor 701 was purchased from Suqian Shengrui New Materials Co., Ltd., CAS No. 2226-96-2; Tetraisopropyl titanate was purchased from Nanjing Tengchuan Technology Co., Ltd. with a purity of ≥99%; Tetraethyl titanate was purchased from Nanjing Tengchuan Technology Co., Ltd. with a purity of ≥99%; Tetrabutyl titanate was purchased from Nanjing Tengchuan Technology Co., Ltd. with a purity of ≥99%; Phosphorus trichloride was purchased from Jinan Huiteng Chemical Co., Ltd. with a purity of ≥99%; 2,2,6,6-Tetramethyl-4-piperidinol was purchased from Suqian Liansheng Technology Co., Ltd., CAS No. 2403-88-5; Acetaldehyde was purchased from Jiangxi Zhongding Biotechnology Co., Ltd. with a purity of ≥99%.

[0021] The present application is further described in detail below with reference to embodiments and comparative examples.

[0022] Reaction equation:

[0023] Example 1.1 A method for preparing polymerization inhibitor ZJ5575 comprises the following steps: 1 mol of triethyl phosphite and 3 mol of inhibitor 701 were added to a reaction bottle, stirred for 30 min to mix the two thoroughly, then 6 g of tetraisopropyl titanate was added and mixed, and the mixture was reacted at 120°C for 11 h, then 500 g of toluene and 500 g of water were added, and the mixture was stirred at 40°C for 2.5 h, and allowed to stand for 30 min for stratification, and the upper organic phase was obtained after removing the lower layer of water, and then water was added to the organic phase again, and negative pressure distillation was performed at 60°C to evaporate the toluene. After the toluene was completely removed, the temperature was lowered to 25°C, and the mixture was centrifuged to obtain a solid, which was dried to obtain inhibitor ZJ5575.

[0024] Example 1.2 A method for preparing polymerization inhibitor ZJ5575 comprises the following steps: 1 mol of triethyl phosphite and 3 mol of inhibitor 701 were added to a reaction bottle, stirred for 30 min to mix the two thoroughly, then 6 g of tetraisopropyl titanate was added and mixed, reacted at 115°C for 12 h, then 500 g of toluene and 500 g of water were added, stirred at 45°C for 2 h, allowed to stand for 30 min for stratification, the lower layer of water was removed to obtain an upper organic phase, then water was added to the organic phase again, negative pressure distillation was performed at 55°C to evaporate the toluene, and after the toluene was completely removed, the temperature was lowered to 22°C, centrifuged to obtain a solid, and dried to obtain inhibitor ZJ5575.

[0025] Example 1.3 A method for preparing polymerization inhibitor ZJ5575 comprises the following steps: 1 mol of triethyl phosphite and 3 mol of inhibitor 701 were added to a reaction bottle, stirred for 30 min to mix the two thoroughly, then 6 g of tetraisopropyl titanate was added and mixed, and the mixture was reacted at 125°C for 10 h, then 500 g of toluene and 500 g of water were added, and the mixture was stirred at 35°C for 2.5 h, and allowed to stand for 30 min for stratification, and the upper organic phase was obtained after removing the lower layer of water, and then water was added to the organic phase again, and negative pressure distillation was performed at 65°C to evaporate the toluene. After the toluene was completely removed, the temperature was lowered to 28°C, and the mixture was centrifuged to obtain a solid, which was dried to obtain inhibitor ZJ5575.

[0026] Example 2.1 A method for preparing polymerization inhibitor ZJ5575 is different from that of Example 1.1 in that the dosage of polymerization inhibitor 701 is 2.8 mol, the molar ratio of triethyl phosphite to polymerization inhibitor 701 is 1:2.8, and the rest is the same as that of Example 1.1.

[0027] Example 2.2 A method for preparing polymerization inhibitor ZJ5575 is different from that of Example 1.1 in that the dosage of polymerization inhibitor 701 is 2.9 mol, the molar ratio of triethyl phosphite to polymerization inhibitor 701 is 1:2.9, and the rest is the same as that of Example 1.1.

[0028] Example 2.3 A method for preparing polymerization inhibitor ZJ5575 is different from that of Example 1.1 in that the dosage of polymerization inhibitor 701 is 3.1 mol, the molar ratio of triethyl phosphite to polymerization inhibitor 701 is 1:3.1, and the rest is the same as that of Example 1.1.

[0029] Example 2.4 A method for preparing polymerization inhibitor ZJ5575 is different from that of Example 1.1 in that the dosage of polymerization inhibitor 701 is 3.2 mol, the molar ratio of triethyl phosphite to polymerization inhibitor 701 is 1:3.2, and the rest is the same as that of Example 1.1.

[0030] Example 2.5 A method for preparing polymerization inhibitor ZJ5575 is different from that of Example 1.1 in that the dosage of polymerization inhibitor 701 is 3.3 mol, the molar ratio of triethyl phosphite to polymerization inhibitor 701 is 1:3.3, and the rest is the same as that of Example 1.1.

[0031] Example 3 A method for preparing a polymerization inhibitor ZJ5575 is different from that of Example 1.1 in that 1 mol of triethyl phosphite is completely replaced by 1 mol of trimethyl phosphite, and the rest is the same as that of Example 1.1.

[0032] Example 4.1 A method for preparing a polymerization inhibitor ZJ5575 is different from that of Example 1.1 in that 6 g of tetraisopropyl titanate is replaced by 6 g of tetraethyl titanate, and the rest is the same as that of Example 1.1.

[0033] Example 4.2 A method for preparing a polymerization inhibitor ZJ5575 is different from that of Example 1.1 in that 6 g of tetraisopropyl titanate is replaced by 6 g of tetrabutyl titanate, and the rest is the same as that of Example 1.1.

[0034] Comparative Example 1 3 mol of inhibitor 701, 2000 g of toluene and 4 mol of triethylamine were put into a four-necked flask with a reflux cooling device, stirring was started, the heating device was turned on, the temperature was raised to 45°C, and phosphorus trichloride toluene solution (a mixture of 1 mol of phosphorus trichloride and 100 g of toluene) was added dropwise for 4.5 hours, and the temperature was kept at 45-50°C. After the addition was completed, the mixture was kept warm for 2 hours, then 1000 g of water was added for washing, stirred at 45°C for 2 hours, and allowed to stand for 30 minutes for stratification; the washing was repeated three times, and after the washing was completed, the lower layer of water was removed to obtain the upper organic phase, and then 3000 g of water was added to the organic phase again, and negative pressure distillation was performed at 55°C to evaporate the toluene. After the toluene was completely removed, the temperature was lowered to 22°C, centrifuged, a solid was obtained, and dried to obtain inhibitor ZJ5575.

[0035] Performance Testing 1. Purity detection: The purity of the polymerization inhibitor ZJ5575 obtained in Examples 1.1-4.2 and Comparative Example 1 was determined by liquid phase detection method, and the results are recorded in Table 1; 2. Wastewater discharge detection: Taking the consumption of the inhibitor 701 as one cycle, the total output wastewater volume of the embodiment and the comparative example in a fixed cycle was measured, and the results were recorded in Table 1.

[0036] Table 1 Performance test table

[0037] Data Analysis: As can be seen from Table 1, the purity of the inhibitor ZJ5575 obtained by the preparation method of Examples 1.1-1.3 of the present application is as high as 98.57-98.58%, and the total output wastewater after the inhibitor 701 is completely consumed is as low as 2200-2300 mL, which proves that the preparation method of the present application does simplify the operation process and significantly reduces the generation of wastewater; In Examples 2.1-2.5, the present application adjusted the dosage of the polymerization inhibitor 701 to 2.8 mol, 2.9 mol, 3.1 mol, 3.2 mol and 3.3 mol, respectively. Compared with the 3 mol polymerization inhibitor 701 used in Example 1.1, it can be clearly seen from the experimental results that when the molar ratio of phosphite to polymerization inhibitor 701 is 1:3, the purity of polymerization inhibitor ZJ5575 is higher, and the total output wastewater volume is also lower, proving that the present application can optimize the reaction conditions by gradually controlling the molar ratio of phosphite to polymerization inhibitor 701, significantly improve the purity of polymerization inhibitor ZJ5575, reduce the generation of by-products, simplify the subsequent treatment process, and thereby effectively reduce the wastewater discharge volume; The purity of the inhibitor ZJ5575 obtained by the preparation method of Example 3 is significantly lower than that of Example 1.1, and the total output wastewater volume is also 400 mL higher than that of Example 1.1, which proves that the present application finally uses triethyl phosphite as a raw material, combined with specific reaction conditions and process flow, compared with trimethyl phosphite, it can further improve the stability and yield of the inhibitor ZJ5575, while significantly reducing the wastewater discharge; The purity of the inhibitor ZJ5575 obtained by the preparation method of Examples 4.1-4.2 is significantly lower than that of Example 1.1, and the total output wastewater volume is also 500-600 mL higher than that of Example 1.1, which proves that the present application uses tetraisopropyl titanate as a catalyst, which can further improve the consistency of catalytic efficiency and the stability of product quality compared with tetraethyl titanate and tetrabutyl titanate, and further promotes the effective contact between the phosphite and the inhibitor 701, improves the selectivity of the reaction between the two, reduces by-products, and improves the purity of the final product. In addition, tetraisopropyl titanate is easier to separate and remove from the final product, simplifies the subsequent treatment process and reduces production costs. At the same time, less wastewater is generated during the use of tetraisopropyl titanate, and it is more environmentally friendly; The purity of the inhibitor ZJ5575 obtained by the preparation method of Comparative Example 1 is significantly lower than that of Example 1.1, and the total output wastewater volume is as high as 6000 mL, which is 270% more than the wastewater volume produced by the preparation method of Example 1.1. This proves that the steps of sequentially reacting phosphite with inhibitor 701 under the action of a catalyst, adding toluene and water for extraction, removing the solvent by negative pressure distillation, and centrifugal drying in the present application can indeed greatly reduce the total output wastewater volume in the process of preparing inhibitor ZJ5575, simplify the operation process, reduce the pressure on environmental protection in the process of preparing inhibitor ZJ5575, and effectively promote the large-scale production and application of inhibitor ZJ5575.

[0038] The embodiments of this specific implementation method are all preferred embodiments of the present application, and are not intended to limit the protection scope of the present application. Therefore, all equivalent changes made based on the structure, shape, and principle of the present application should be included in the protection scope of the present application.

Claims

1. A method for preparing polymerization inhibitor ZJ5575, characterized in that: The method comprises the following steps: mixing phosphite, inhibitor 701 and a catalyst, reacting at a temperature of 115-125°C for 10-12h, then adding toluene and water, stirring at a temperature of 35-45°C for 2-2.5h, standing for stratification to obtain an upper organic phase, then adding water to the organic phase again, performing negative pressure distillation at a temperature of 55-65°C, cooling to 22-28°C after toluene is completely removed, centrifuging to obtain a solid, and drying to obtain an inhibitor ZJ5575, wherein the phosphite is one of triethyl phosphite and trimethyl phosphite.

2. The method for preparing a polymerization inhibitor ZJ5575 according to claim 1, characterized in that: The phosphite is triethyl phosphite.

3. The preparation method of a polymerization inhibitor ZJ5575 according to claim 1, characterized in that: The molar ratio of the phosphite to the inhibitor 701 is 1:(2.8-3.3).

4. The method for preparing a polymerization inhibitor ZJ5575 according to claim 3, characterized in that: The molar ratio of the phosphite to the inhibitor 701 is 1:(2.9-3.2).

5. The method for preparing a polymerization inhibitor ZJ5575 according to claim 4, characterized in that: The molar ratio of the phosphite to the inhibitor 701 is 1:

3.

6. The method for preparing a polymerization inhibitor ZJ5575 according to claim 1, characterized in that: The catalyst includes any one of tetraisopropyl titanate, tetraethyl titanate and tetrabutyl titanate.

7. The method for preparing a polymerization inhibitor ZJ5575 according to claim 6, characterized in that: The catalyst is tetraisopropyl titanate.

8. A polymerization inhibitor ZJ5575 prepared by the preparation method according to any one of claims 1 to 7.

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