Process for the preparation of antioxidant 168 and its use
By using the solid base catalyst NA-ZSM-5 molecular sieve to react with 2,4-di-tert-butylphenol and phosphorus trichloride, combined with adsorption treatment and simple post-treatment steps, the problems of difficult separation and low purity of antioxidant 168 were solved, realizing the preparation of antioxidants with high purity and low acid value, which has good prospects for industrial application.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- YING KOU SHI FENG GUANG HUA GONG YOU XIAN GONG SI
- Filing Date
- 2023-09-21
- Publication Date
- 2026-06-02
AI Technical Summary
The existing technology for preparing antioxidant 168 has problems of separation difficulties and low purity, especially the use of organic amines as catalysts, which leads to high acid value and low purity.
Using solid alkali catalyst NA-ZSM-5 molecular sieve as the catalyst, antioxidant 168 is generated by reacting with 2,4-di-tert-butylphenol and phosphorus trichloride. The antioxidant is then adsorbed using a solid alkali catalyst bed. Combined with desolvation, crystallization and drying steps, the post-processing is simplified.
It improves the purity of antioxidant 168 and reduces the acid value, simplifies the process, reduces wastewater treatment steps, and has better industrial applicability.
Smart Images
Figure FT_1
Abstract
Description
Technical Field
[0001] This invention relates to the field of compound synthesis technology, and specifically to a method for preparing antioxidant 168 and its application. Background Technology
[0002] Antioxidant 168 (C 42 H 63 The Chinese name for O3P is tris[2,4-di-tert-butylphenyl]phosphite, with a relative molecular weight of 647. It belongs to the phosphite antioxidant class. When used in polyethylene, polypropylene, and rubber, it slows down the oxidation process of polymer products, thereby increasing their lifespan. The mechanism by which antioxidant 168 slows down the oxidation of polymer products is mainly through the decomposition of peroxides generated during the oxidation process to produce stable and bioactive products. Antioxidant 168 is often used as an auxiliary antioxidant in combination with other antioxidants, such as antioxidant 1010, to better extend the lifespan of polymer products.
[0003] With the increasing demand for polymer products in the market, antioxidants, as indispensable additives in the processing of polymer products that can extend the lifespan of polymers, are in high demand.
[0004] The demand for antioxidant 168, a high-performance antioxidant, has also increased significantly.
[0005] The catalyst used in patent CN110590834A can be easily, quickly and completely separated from the system after the reaction is completed. It can be used continuously without generating solid waste, effectively improving the quality of antioxidant 168 products and reducing environmental pollution.
[0006] Currently, organic amines are commonly used as catalysts to prepare antioxidant 168. However, organic amines present challenges in subsequent separation, resulting in antioxidant 168 with high acid value and low purity. Attached Figure Description
[0007] Figure 1 The image shows the liquid chromatogram of antioxidant 168 prepared in Example 1. Summary of the Invention
[0008] The purpose of this invention is to overcome the problems of difficult separation and low purity in the preparation of antioxidant 168 in the prior art, and to provide a new preparation method and application of antioxidant 168.
[0009] The first aspect of this invention provides a method for preparing antioxidant 168, the method comprising:
[0010] (1) 2,4-di-tert-butylphenol, a first organic solvent and a solid base catalyst are added to the reactor to form a first mixture. Then, a second mixture containing phosphorus trichloride and a second solvent is added to the first mixture at 30-40°C to carry out the first reaction and obtain the first product stream and HCl gas.
[0011] (2) The first product stream is subjected to adsorption treatment in a solid base catalyst bed to obtain a product stream containing antioxidant 168;
[0012] (3) The product stream containing antioxidant 168 is subjected to solvent removal, crystallization, filtration and drying to obtain antioxidant 168.
[0013] Preferably, the preparation method of the solid base catalyst includes:
[0014] S1 Weigh 100 parts by weight of NA-ZSM-5 molecular sieve, 20-30 parts of water, 30-40 parts of binder, and 5-12 parts of extrusion aid, and knead them to obtain a mixture.
[0015] S2 The mixture is extruded into strips with a diameter of 4-6mm, and then cut into strip-shaped products by a strip cutting device. After being fed into a shaping machine, it is sheared, rounded and dried into spherical materials with a diameter of 3-4mm. The spherical materials are dried A and calcined A to obtain the carrier.
[0016] S3. Take 100 parts of the support from step S2, 10-20 parts of magnesium nitrate aqueous solution with a mass concentration of 15-20%, and 8-12 parts of chromium chloride aqueous solution with a mass concentration of 15-20% according to the weight, mix them evenly, and then dry B and calcine B to obtain a solid base catalyst.
[0017] Preferably, the first organic solvent is selected from at least one of benzene, toluene, ethylbenzene, and diethylbenzene.
[0018] Preferably, the second solvent is selected from at least one of benzene, diethyl ether, toluene, chloroform, and tetrahydrofuran.
[0019] Preferably, in the first mixture, the mass ratio of 2,4-di-tert-butylphenol to the first organic solvent is 1:(0.3-0.8).
[0020] Preferably, in the first mixture, the mass ratio of 2,4-di-tert-butylphenol to the solid base catalyst is (20-30):1.
[0021] Preferably, in the second mixture, the mass ratio of phosphorus trichloride to the second solvent is 1:(0.5-2); and the molar ratio of 2,4-di-tert-butylphenol to phosphorus trichloride is (3-4):1.
[0022] Preferably, the second mixture is added dropwise.
[0023] Preferably, the conditions for the first reaction include: a reaction temperature of 70-105°C and a reaction time of 1.5-3 hours.
[0024] Preferably, in step (2), the conditions for adsorption treatment include: room temperature, and a liquid hourly space velocity (LHSV) of 2-10 h⁻¹ for the first product stream. -1 .
[0025] The second aspect of the present invention provides the application of antioxidant 168 prepared by the preparation method described herein in polypropylene.
[0026] Compared with the prior art, the present invention has at least the following beneficial effects:
[0027] (1) The post-treatment is simple, reducing the steps of process wastewater treatment and making it more practical for industrial use;
[0028] (2) Antioxidant 168 has high purity;
[0029] (3) Antioxidant 168 has a low acid value;
[0030] (4) Antioxidants can be used in polypropylene to better improve the performance of polypropylene. Detailed Implementation
[0031] The invention will be more readily understood by referring to the following detailed description of preferred embodiments and included examples. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In case of conflict, the definitions in this specification shall prevail.
[0032] The first aspect of this invention provides a method for preparing antioxidant 168, the method comprising:
[0033] (1) 2,4-di-tert-butylphenol, a first organic solvent and a solid base catalyst are added to the reactor to form a first mixture. Then, a second mixture containing phosphorus trichloride and a second solvent is added to the first mixture at 30-40°C to carry out the first reaction and obtain the first product stream and HCl gas.
[0034] (2) The first product stream is subjected to adsorption treatment in a solid base catalyst bed to obtain a product stream containing antioxidant 168;
[0035] (3) The product stream containing antioxidant 168 is subjected to solvent removal, crystallization, filtration and drying to obtain antioxidant 168.
[0036] In this invention, phosphorus trichloride is first dissolved in a solvent, and then added to a system containing 2,4-di-tert-butylphenol and organic amine. During the first reaction, the heat dissipation of the reaction system is accelerated, reducing the occurrence of side reactions. Furthermore, the applicant unexpectedly discovered that after passing the first product stream through a solid base catalyst, antioxidant 168 with low acid value can be obtained without washing or other steps, reducing the need for process wastewater treatment and other steps, thus having better industrial applicability.
[0037] In one embodiment, the method for preparing the solid base catalyst includes:
[0038] S1 Weigh 100 parts by weight of NA-ZSM-5 molecular sieve, 20-30 parts of water, 30-40 parts of binder, and 5-12 parts of extrusion aid, and knead them to obtain a mixture.
[0039] S2 The mixture is extruded into strips with a diameter of 4-6mm, and then cut into strip-shaped products by a strip cutting device. After being fed into a shaping machine, it is sheared, rounded and dried into spherical materials with a diameter of 3-4mm. The spherical materials are dried A and calcined A to obtain the carrier.
[0040] S3. Take 100 parts of the support from step S2, 10-20 parts of magnesium nitrate aqueous solution with a mass concentration of 15-20%, and 8-12 parts of chromium chloride aqueous solution with a mass concentration of 15-20% according to the weight, mix them evenly, and then dry B and calcine B to obtain a solid base catalyst.
[0041] In this invention, the solid base catalyst is alkaline, which not only catalyzes the reaction of 2,4-di-tert-butylphenol with phosphorus trichloride to better generate antioxidant 168, but also allows the solid base catalyst to remain in the reactor for the next reaction, exhibiting good recyclability. In experiments, the inventors discovered that the amount of magnesium nitrate and chromium chloride added should be strictly controlled during the preparation of the solid base catalyst. This is likely because excessive addition leads to a stronger alkalinity of the solid base, resulting in excessive side reactions, while insufficient addition fails to effectively catalyze the reaction of 2,4-di-tert-butylphenol with phosphorus trichloride. Furthermore, the use of magnesium and chromium as active ingredients in this invention, working synergistically with the support, enhances the catalytic effect.
[0042] In one embodiment, the binder is selected from at least one of silica sol, alumina sol, and kaolin, preferably silica sol.
[0043] In one embodiment, the concentration of silica in the silica sol is 30-45%, preferably 40%.
[0044] In one embodiment, the extrusion aid is selected from at least one of guar gum powder, methylcellulose, polyvinyl alcohol, and starch, preferably guar gum powder.
[0045] In one embodiment, the NA-ZSM-5 molecular sieve was purchased from Zhuoran Environmental Protection Technology (Dalian) Co., Ltd.
[0046] In one embodiment, in step S2, the drying conditions for drying A include: vacuum drying at 60-80°C for 8-12 hours.
[0047] In one embodiment, in step S2, the conditions for calcining A include: calcining at 400-500°C for 3-5 hours in an air atmosphere.
[0048] In one embodiment, in step S3, the drying conditions for drying B include: drying at 120-150°C for 10-15 hours.
[0049] In one embodiment, the conditions for calcining B in step S3 include: calcining at 500-600°C for 8-12 hours in an inert atmosphere.
[0050] In one embodiment, the first organic solvent is selected from at least one of benzene, toluene, ethylbenzene, and diethylbenzene, preferably toluene.
[0051] In one embodiment, the second solvent is selected from at least one of benzene, diethyl ether, toluene, chloroform, and tetrahydrofuran, preferably toluene.
[0052] In one embodiment, the mass ratio of 2,4-di-tert-butylphenol to the first organic solvent in the first mixture is 1:(0.3-0.8), for example, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9 or 1:1, preferably 1:(0.6-0.8).
[0053] In one embodiment, the mass ratio of 2,4-di-tert-butylphenol to solid base catalyst in the first mixture is (20-30):1, for example, 20:1, 22:1, 24:1, 27:1, 28:1 or 30:1, preferably (22-25):1.
[0054] In one embodiment, the mass ratio of phosphorus trichloride to the second solvent in the second mixture is 1:(0.5-2), for example 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1.0, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2.0, preferably 1:(1-1.5).
[0055] In this invention, when preparing a second mixture containing phosphorus trichloride and a second solvent using phosphorus trichloride and a second solvent, the preparation is generally carried out at 0-5°C.
[0056] In one embodiment, the molar ratio of 2,4-di-tert-butylphenol to phosphorus trichloride is (3-4):1, for example 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1, or 4:1, preferably (3.1-3.3):1.
[0057] In this invention, the generated HCl gas can be discharged through the back pressure valve of the reactor and then processed by an external HCl treatment device. This invention does not impose any special restrictions on this, and will not elaborate further in this invention.
[0058] In one embodiment, the second mixture is added by dripping, and the dripping speed is not particularly limited, but preferably it is completed within 1-1.5 hours, and the dripping speed tends to be uniform.
[0059] In this invention, compared with the prior art, the second mixture containing phosphorus trichloride can be delivered more quickly, which is beneficial to the production process and saves time costs.
[0060] In one embodiment, the conditions for the first reaction include: a reaction temperature of 70-105°C (e.g., 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, 100°C, or 105°C) and a reaction time of 1.5-3 hours (e.g., 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours, or 3 hours).
[0061] In a preferred embodiment, the conditions for the first reaction include: a reaction temperature of 80-90°C and a reaction time of 2-2.5 hours.
[0062] In this invention, the calculation for the first reaction begins after the second mixture has been added.
[0063] In this invention, by controlling the ratio of each raw material and solvent as well as the reaction conditions, antioxidant 168 can be synthesized more efficiently, and the generation of by-products can be reduced, thereby reducing the subsequent purification process and obtaining antioxidant 168 with higher purity and lower acidity.
[0064] In this invention, after step (1) is completed, the first product stream in liquid phase can be directly introduced and left in the reactor as a solid base catalyst in solid phase for the next reaction.
[0065] In one embodiment, the conditions for adsorption treatment in step (2) include: room temperature, and a liquid hourly space velocity (LHSV) of 2-10 h⁻¹ for the first product stream. -1 For example, 2h -1 3h -1 4h -1 5h -1 6h -1 7h -1 8h -1 9h -1 or 10h -1 Preferably 4-6h -1 .
[0066] In this invention, by controlling the adsorption process, the acid value in antioxidant 168 can be reduced more effectively.
[0067] In this invention, it is understood that the specific operation of adsorbing the first product stream through a solid alkali catalyst bed is as follows: the first product stream is introduced into a fixed bed containing a solid alkali catalyst for adsorption treatment.
[0068] Furthermore, in this invention, the inventors have discovered that treating the first product stream through a solid alkali catalyst bed improves the purity of antioxidant 168, possibly because the solid alkali catalyst can adsorb some phenolic impurities to a certain extent, reducing the difficulty of subsequent separation.
[0069] In one embodiment, the product stream containing antioxidant 168 also contains a first solvent and a second solvent. The specific method for removing the first solvent and the second solvent is not particularly limited, for example, the first solvent and the second solvent can be recovered by vacuum distillation. The present invention has no particular limitation in this regard.
[0070] In one embodiment, the crystallization method in step (3) includes: adding the solid material obtained by desolventizing to a mixed solvent of isopropanol and methyl tert-butyl ether in a reaction vessel, stirring at 50-70°C for 0.5-1 hour, and then cooling to room temperature.
[0071] In a preferred embodiment, the drying conditions in step (3) are vacuum drying at 35-50°C for 5-10 hours.
[0072] In a preferred embodiment, the solid material : mixed solvent = 1g : (5-10)mL.
[0073] In a preferred embodiment, the volume ratio of isopropanol to methyl tert-butyl ether is (3-6):1, for example 3:1, 4:1, 5:1 or 6:1.
[0074] The second aspect of the present invention provides the application of antioxidant 168 prepared by the preparation method described herein in polypropylene.
[0075] Those skilled in the art will know that antioxidant 168 is a high-performance phosphite antioxidant with strong anti-extraction properties, stability against hydrolysis, and significant improvement in the light stability of products. It can be used in combination with various phenolic antioxidants. Antioxidant 168 belongs to the auxiliary antioxidant class and is often used in combination with antioxidant 1010. In one embodiment, antioxidant 168 prepared according to this invention is combined with antioxidant 1010 to obtain an antioxidant mixture. Then, the antioxidant mixture is added to polypropylene powder and mixed evenly. After extrusion, granulation, and drying, modified polypropylene is obtained.
[0076] In a preferred embodiment, the mass ratio of antioxidant 1010 to antioxidant 168 is 1:(1-3).
[0077] In a preferred embodiment, the antioxidant mixture is 0.5-1.5 wt% of the polypropylene powder, preferably 0.8 wt%.
[0078] In one embodiment, the extrusion conditions include: the temperatures of each zone of the extruder are 170°C, 190°C, 205°C, 210°C, 210°C, 210°C, 210°C, and 205°C, respectively; the die head temperature is 185°C; the main extruder speed is 120 r / min; and the feed speed is 15 r / min.
[0079] The melt flow index of polyolefin materials can often be used to evaluate their antioxidant properties. In this invention, the addition of antioxidant 168 can reduce the breakage of polypropylene molecular chains and effectively inhibit the thermo-oxidative aging phenomenon during polypropylene processing.
[0080] The present invention will be described in detail below through examples. The NA-ZSM-5 molecular sieve described in the following examples was purchased from Zhuoran Environmental Protection Technology (Dalian) Co., Ltd.
[0081] Preparation Example 1
[0082] S1 Weigh 100 parts by weight of NA-ZSM-5 molecular sieve, 20 parts of water, 35 parts of silica sol with a mass concentration of 40%, and 12 parts of guar gum powder and knead them together to obtain a mixture.
[0083] S2 The mixture is extruded into strips with a diameter of 5mm, and then cut into strip column products by a strip cutting device. After being fed into a shaping machine, it is sheared, rounded and dried into spherical materials with a diameter of 4mm. The spherical materials are vacuum dried at 70℃ for 10h and calcined at 450℃ in air for 5h to obtain the carrier.
[0084] S3. Take 100 parts of the support, 15 parts of magnesium nitrate aqueous solution with a mass concentration of 20% and 10 parts of chromium chloride aqueous solution with a mass concentration of 20% according to the weight, mix them evenly, dry at 145℃ for 12h and calcine at 550℃ for 10h in an inert atmosphere to obtain solid base catalyst A.
[0085] Preparation Example 2
[0086] S1 Weigh 100 parts by weight of NA-ZSM-5 molecular sieve, 30 parts of water, 40 parts of silica sol with a mass concentration of 40%, and 10 parts of guar gum powder and knead them together to obtain a mixture.
[0087] S2 The mixture is extruded into strips with a diameter of 5mm, and then cut into strip column products by a strip cutting device. After being fed into a shaping machine, it is sheared, rounded and dried into spherical materials with a diameter of 4mm. The spherical materials are vacuum dried at 80℃ for 8h and calcined at 500℃ in air for 4h to obtain the carrier.
[0088] S3. Take 100 parts of the support, 20 parts of magnesium nitrate aqueous solution with a mass concentration of 15% and 8 parts of chromium chloride aqueous solution with a mass concentration of 20% according to the weight, mix them evenly, dry at 150℃ for 10h and calcine at 600℃ for 8h in an inert atmosphere to obtain solid base catalyst B.
[0089] Example 1
[0090] Preparation of Antioxidant 168:
[0091] (1) 960g of 2,4-di-tert-butylphenol, 580g of toluene and 40g of solid base catalyst A were added to the reactor to form a first mixture. Then, a second mixture containing 206g of phosphorus trichloride and 250g of toluene was added dropwise to the first mixture at 35°C. The addition was completed in 1.5 hours. After the addition was completed, the mixture was reacted at 85°C for 2 hours to obtain the first product stream and HCl gas.
[0092] (2) The first product stream is introduced into a fixed bed containing solid base catalyst A for adsorption treatment. The liquid hourly space velocity (LHSV) of the first product stream is 5 h⁻¹. -1 The adsorption temperature was room temperature to obtain a product stream containing antioxidant 168;
[0093] (3) The product containing antioxidant 168 was distilled under reduced pressure to obtain a solid material. In a reactor, a mixture of isopropanol and methyl tert-butyl ether in a ratio of 5:1 (w / v) was added to the solid material and stirred at 60°C for 0.5 hours. After cooling to room temperature, the mixture was filtered and the solid obtained was vacuum dried at 40°C for 8 hours to obtain antioxidant 168.
[0094] Antioxidant 168 has an acid value of 0.01 mg KOH / g and an HPCL purity of 99.93%.
[0095] The prepared antioxidant 168 was subjected to liquid phase testing under the following conditions:
[0096] Instrument: Shimadzu LC-20AD; Column: Ultimate AQ-C18 4.6*100mm 3um; Flow rate: 1.5ml / min; Column temperature: 30℃; Detection wavelength: 275nm; Injection volume: 5ul; Mobile phase A: Water; Mobile phase B: Acetonitrile-tetrahydrofuran = 1:1
[0097] The gradients are shown in the table below:
[0098] time A（%） B（%） 0 15 85 2 15 85 8 0 100 10 0 100 10.1 15 85 15 15 85
[0099] Sample preparation: Dissolve an appropriate amount of mobile phase B.
[0100] The liquid chromatogram of antioxidant 168 is as follows: Figure 1 As shown.
[0101] Example 2
[0102] Preparation of Antioxidant 168:
[0103] (1) 1071g of 2,4-di-tert-butylphenol, 750g of toluene and 47g of solid base catalyst B were added to the reactor to form a first mixture. Then, a second mixture containing 230g of phosphorus trichloride and 260g of toluene was added dropwise to the first mixture at 35°C. The addition was completed in 1.5 hours. After the addition was completed, the mixture was reacted at 85°C for 2 hours to obtain the first product stream and HCl gas.
[0104] (2) The first product stream is introduced into a fixed bed containing solid base catalyst B for adsorption treatment. The liquid hourly space velocity (LHSV) of the first product stream is 4 h⁻¹. -1 The adsorption temperature was room temperature to obtain a product stream containing antioxidant 168;
[0105] (3) The product containing antioxidant 168 was distilled under reduced pressure to obtain a solid material. In a reactor, a mixture of isopropanol and methyl tert-butyl ether in a ratio of 6:1 (w / v) was added to the solid material and stirred at 50°C for 1 hour. After cooling to room temperature, the mixture was filtered and the solid obtained was vacuum dried at 40°C for 8 hours to obtain antioxidant 168.
[0106] Antioxidant 168 has an acid value of 0.01 mg KOH / g and an HPCL purity of 99.9%. Example 3
[0107] Preparation of Antioxidant 168:
[0108] (1) 1071g of 2,4-di-tert-butylphenol, 750g of toluene and 47g of solid base catalyst A were added to the reactor to form a first mixture. Then, a second mixture containing 230g of phosphorus trichloride and 260g of toluene was added dropwise to the first mixture at 35°C. The addition was completed in 1.5 hours. After the addition was completed, the mixture was reacted at 85°C for 2 hours to obtain the first product stream and HCl gas.
[0109] (2) The first product stream is introduced into a fixed bed containing solid base catalyst A for adsorption treatment. The liquid hourly space velocity (LHSV) of the first product stream is 5 h⁻¹. -1 The adsorption temperature was room temperature to obtain a product stream containing antioxidant 168;
[0110] (3) The product containing antioxidant 168 was distilled under reduced pressure to obtain a solid material. In a reactor, a mixture of isopropanol and methyl tert-butyl ether in a ratio of 4:1 (w / v) was added to the solid material and stirred at 50°C for 1 hour. After cooling to room temperature, the mixture was filtered and the solid obtained was vacuum dried at 40°C for 8 hours to obtain antioxidant 168.
[0111] Antioxidant 168 has an acid value of 0.01 mg KOH / g and an HPCL purity of 99.91%. Example 4
[0112] (1) 1071g of 2,4-di-tert-butylphenol, 750g of toluene and 107g of solid base catalyst A were added to the reactor to form a first mixture. Then, a second mixture containing 230g of phosphorus trichloride and 260g of toluene was added dropwise to the first mixture at 35°C. The addition was completed in 1.5 hours. After the addition was completed, the mixture was reacted at 85°C for 2 hours to obtain the first product stream and HCl gas.
[0113] (2) The first product stream is introduced into a fixed bed containing solid base catalyst A for adsorption treatment. The liquid hourly space velocity (LHSV) of the first product stream is 5 h⁻¹. -1The adsorption temperature was room temperature to obtain a product stream containing antioxidant 168;
[0114] (3) The product containing antioxidant 168 was distilled under reduced pressure to obtain a solid material. In a reactor, a mixture of isopropanol and methyl tert-butyl ether in a ratio of 4:1 (w / v) was added to the solid material and stirred at 50°C for 1 hour. After cooling to room temperature, the mixture was filtered and the solid obtained was vacuum dried at 40°C for 8 hours to obtain antioxidant 168.
[0115] Antioxidant 168 has an acid value of 0.02 mg KOH / g and an HPCL purity of 99.78%. Example 5
[0116] (1) 1071g of 2,4-di-tert-butylphenol, 750g of toluene and 30g of solid base catalyst A were added to the reactor to form a first mixture. Then, a second mixture containing 230g of phosphorus trichloride and 260g of toluene was added dropwise to the first mixture at 35°C. The addition was completed in 1.5 hours. After the addition was completed, the mixture was reacted at 85°C for 2 hours to obtain the first product stream and HCl gas.
[0117] (2) The first product stream is introduced into a fixed bed containing solid base catalyst A for adsorption treatment. The liquid hourly space velocity (LHSV) of the first product stream is 5 h⁻¹. -1 The adsorption temperature was room temperature to obtain a product stream containing antioxidant 168;
[0118] (3) The product containing antioxidant 168 was distilled under reduced pressure to obtain a solid material. In a reactor, a mixture of isopropanol and methyl tert-butyl ether in a ratio of 4:1 (w / v) was added to the solid material and stirred at 50°C for 1 hour. After cooling to room temperature, the mixture was filtered and the solid obtained was vacuum dried at 40°C for 8 hours to obtain antioxidant 168.
[0119] Antioxidant 168 has an acid value of 0.05 mg KOH / g and an HPCL purity of 99.82%.
[0120] Example 6
[0121] (1) 1071g of 2,4-di-tert-butylphenol, 750g of toluene and 47g of solid base catalyst A were added to the reactor to form a first mixture. Then, a second mixture containing 230g of phosphorus trichloride and 260g of toluene was added dropwise to the first mixture at 35°C. The addition was completed in 1.5 hours. After the addition was completed, the mixture was reacted at 85°C for 2 hours to obtain the first product stream and HCl gas.
[0122] (2) The first product stream is introduced into a fixed bed containing solid base catalyst A for adsorption treatment. The liquid hourly space velocity (LHSV) of the first product stream is 5 h⁻¹. -1 The adsorption temperature was room temperature to obtain a product stream containing antioxidant 168;
[0123] (3) The product containing antioxidant 168 was distilled under reduced pressure to obtain a solid material. In the reactor, five times its weight volume of isopropanol (w / v) was added to the solid material and stirred at 50°C for 1 hour. After cooling to room temperature, the solid was filtered and dried under vacuum at 40°C for 8 hours to obtain antioxidant 168.
[0124] Antioxidant 168 has an acid value of 0.01 mg KOH / g and an HPCL purity of 99.72%.
[0125] Comparative Example 1
[0126] (1) 1071g of 2,4-di-tert-butylphenol, 750g of toluene and 47g of solid base catalyst A were added to the reactor to form a first mixture. Then, a second mixture containing 230g of phosphorus trichloride and 260g of toluene was added dropwise to the first mixture at 35°C. The addition was completed in 1.5 hours. After the addition was completed, the mixture was reacted at 85°C for 2 hours to obtain the first product stream and HCl gas.
[0127] (2) The first product stream was distilled under reduced pressure to obtain a solid material. In the reactor, five times its weight volume of (w / v) isopropanol and methyl tert-butyl ether = 4:1 mixed solvent (v / v) were added to the solid material and stirred at 50°C for 1 hour. After that, it was cooled to room temperature and filtered. The solid obtained by filtration was dried under vacuum at 40°C for 8 hours to obtain antioxidant 168.
[0128] Antioxidant 168 has an acid value of 0.28 mg KOH / g and an HPCL purity of 99.32%.
[0129] Application Example 1
[0130] In Example 1, antioxidant 168 and antioxidant 1010 were compounded (mass ratio 1:3) to obtain an antioxidant mixture. Then, the antioxidant mixture (0.8 wt% of the polypropylene powder) was added to the polypropylene powder and mixed evenly. After extrusion, granulation, and drying, modified polypropylene was obtained. The extrusion conditions included: the temperatures of each zone of the extruder were 170℃, 190℃, 205℃, 210℃, 210℃, 210℃, 210℃, and 205℃, respectively; the die head temperature was 185℃; the main machine speed was 120 r / min; and the feeding speed was 15 r / min.
[0131] The melt index (230℃, 2.16kg) of the modified polypropylene is 2.92g / 10min.
[0132] Application Example 2
[0133] In Example 4, antioxidant 168 and antioxidant 1010 were compounded (mass ratio of 1:3) to obtain an antioxidant mixture (mass of 0.8 wt% of polypropylene powder). The antioxidant mixture was then added to the polypropylene powder (same as in Application Example 1) and mixed evenly. After extrusion, granulation, and drying, modified polypropylene was obtained. The extrusion conditions included: temperatures of each zone of the extruder were 170°C, 190°C, 205°C, 210°C, 210°C, 210°C, 210°C, 210°C, and 205°C, respectively; the die head temperature was 185°C; the main machine speed was 120 r / min; and the feed speed was 15 r / min.
[0134] The melt index (230℃, 2.16kg) of the modified polypropylene is 3.82g / 10min.
[0135] Comparative Application Example 1
[0136] After being mixed evenly with polypropylene powder (same as in Application Example 1), modified polypropylene was obtained by extrusion, granulation, and drying. The extrusion conditions included: the temperatures of each zone of the extruder were 170℃, 190℃, 205℃, 210℃, 210℃, 210℃, 210℃, and 205℃, respectively; the die head temperature was 185℃; the main machine speed was 120 r / min; and the feeding speed was 15 r / min.
[0137] The melt index (230℃, 2.16kg) of the modified polypropylene is 11.2g / 10min.
[0138] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.
Claims
1. A process for the preparation of antioxidant 168, characterized in that, The preparation method includes: (1) 2,4-di-tert-butylphenol, a first organic solvent and a solid base catalyst are added to the reactor to form a first mixture. Then, a second mixture containing phosphorus trichloride and a second solvent is added to the first mixture at 30-40°C to carry out the first reaction and obtain the first product stream and HCl gas. (2) The first product stream is subjected to adsorption treatment in a solid base catalyst bed to obtain a product stream containing antioxidant 168; (3) The product stream containing antioxidant 168 is subjected to solvent removal, crystallization, filtration and drying to obtain antioxidant 168; The preparation method of the solid base catalyst includes: S1 Weigh 100 parts by weight of NA-ZSM-5 molecular sieve, 20-30 parts of water, 30-40 parts of binder, and 5-12 parts of extrusion aid, and knead them to obtain a mixture. S2 The mixture is extruded into strips with a diameter of 4-6mm, and then cut into strip-shaped products by a strip cutting device. After being fed into a shaping machine, it is sheared, rounded and dried into spherical materials with a diameter of 3-4mm. The spherical materials are then dried and calcined to obtain the carrier. S3. Take 100 parts of the support from step S2, 10-20 parts of magnesium nitrate aqueous solution with a mass concentration of 15-20%, and 8-12 parts of chromium chloride aqueous solution with a mass concentration of 15-20% according to the weight, mix them evenly, and then dry and calcine to obtain a solid base catalyst. The first organic solvent is selected from at least one of benzene, toluene, ethylbenzene, and diethylbenzene; the second solvent is selected from at least one of benzene, diethyl ether, toluene, chloroform, and tetrahydrofuran.
2. The preparation method according to claim 1, characterized in that, In the first mixture, the mass ratio of 2,4-di-tert-butylphenol to the first organic solvent is 1:(0.3-0.8).
3. The preparation method according to claim 1, characterized in that, In the first mixture, the mass ratio of 2,4-di-tert-butylphenol to the solid base catalyst is (20-30):
1.
4. The preparation method according to claim 1, characterized in that, In the second mixture, the mass ratio of phosphorus trichloride to the second solvent is 1:(0.5-2); the molar ratio of 2,4-di-tert-butylphenol to phosphorus trichloride is (3-4):
1.
5. The preparation method according to claim 1, characterized in that, The second mixture is added dropwise.
6. The preparation method according to claim 1, characterized in that, The conditions for the first reaction include: a reaction temperature of 70-105℃ and a reaction time of 1.5-3 hours.
7. The preparation method according to claim 1, characterized in that, In step (2), the conditions for the adsorption treatment include: room temperature, a liquid hourly space velocity (LHSV) of the first product stream of 2-10 h -1 .