CN116284141A - Preparation method of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite - Google Patents
Preparation method of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite Download PDFInfo
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Abstract
The invention provides a preparation method of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, which comprises the steps of firstly mixing pentaerythritol, phosphorus trichloride, a solvent and a catalyst, and performing a preliminary reaction to obtain an intermediate; wherein the catalyst comprises a first component: urotropin and a second component: trimethylamine and/or triethylamine; and then dropwise adding cumylphenol to continue the pre-program temperature control and pressure control reaction, then carrying out the decompression reaction, removing the solvent and carrying out the refining post-treatment, and controlling the reaction stably and efficiently by the subsequent reaction of the intermediate and the cumylphenol, the decompression reaction and the matching of the solvent removal and the refining post-treatment operation, so that the conversion rate and the product quality of the product are further improved, the quality improvement and the efficiency improvement are realized, and the product is used as an antioxidant in the polymer, and the oxidation resistance of the polymer can be improved.
Description
Technical Field
The invention relates to the technical field of preparation of antioxidants for high polymer materials, in particular to a preparation method of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
Background
The polymer is easy to be oxidized by oxygen in air under the action of light and heat in the processing and long-term use processes, so that the polymer has the disadvantages of losing physical properties, changing color, cracking, losing glossiness and the like, and the appearance becomes unaesthetic, so that an antioxidant is required to be added to improve the processing stability and long-term stability of the polymer. Antioxidants, when present in small amounts in polymer systems, retard or inhibit the progress of the oxidation process of the polymer, thereby preventing the aging of the polymer and extending its useful life, also known as "antioxidants".
The antioxidant mainly comprises hindered phenol antioxidants, phosphite antioxidants or thio antioxidants, etc. The phosphite antioxidant is a processing stabilizer antioxidant with excellent performance, not only improves the processing stability of the polymer and protects the stability of the polymer in the processing process, but also has good color stability, and has wide application in high polymer materials such as polyolefin, styrene polymer or polyvinyl chloride, and the like, and the existing typical products comprise antioxidant 168, TNPP, 626, and the like. 168 and 626 are high-melting-point solid phosphite antioxidants, TNPP is liquid phosphite antioxidants, and nonylphenol which is one of main raw materials for synthesizing TNPP can cause female phenomenon of male fishes at the downstream of a sewage treatment plant, and is an endocrine disrupter or environmental hormone organic matter with estrogen effect. Through researches, nonylphenol has an interference effect on endocrine of human and wild animals, so TNPP using nonylphenol as a main raw material is gradually limited. The antioxidant 168 has the advantage of low production cost as the antioxidant with the largest sales volume, but has general application performance and poor high temperature resistance, and can not meet the high performance requirement of high-end products. In contrast, the antioxidant 626 has good application performance, but still cannot meet the processing requirements of high-end products, has poor hydrolysis resistance and is very easy to hydrolyze.
At present, the antioxidant bis (2, 4-dicumylphenyl) pentaerythritol diphosphite has the advantages of high molecular weight, low volatility, high phosphorus content (7.3%), large molecular weight (852) and high melting point (220-230 ℃), has remarkable anti-yellowing and high-temperature degradation protection effects in the processing process, has excellent high-temperature stability and low volatility at high temperature, and is widely applied to polymer materials and products with high requirements on thermal stability, such as engine accessories and radiators in the automotive field, dish washers, ovens, microwave ovens, dryers and the like in household appliances, and the materials are required to be resistant to high temperature, brittle fracture and yellowing. The bis (2, 4-dicumylphenyl) pentaerythritol diphosphite can maintain the hydrolytic stability even if exposed to a humid environment, and the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite cannot generate coking like other phosphite products due to the good hydrolytic resistance, so that the black spots of the polymer appear and the filter screen of an extrusion system is blocked, and the production processing and the product quality are affected. Meanwhile, the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite can show good color and melt processing stability at different processing temperatures, can still well protect the color and melt stability of products under the condition of multiple extrusion, and has good application prospects in the plastic modification industry, particularly in the engineering plastic fields such as PC, PA polyamide (nylon), PET, PBT polyester, PPO, PPS, polyether and the like due to the extraordinary high-temperature stability.
However, the existing antioxidant bis (2, 4-dicumylphenyl) pentaerythritol diphosphite has fewer industrialized products, and the main reasons are that the product has large molecular weight and large preparation difficulty, the existing production technology is immature, the energy consumption is high, the product conversion rate is low, and the quality is unstable.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing bis (2, 4-dicumylphenyl) pentaerythritol diphosphite. The preparation method provided by the invention can accelerate the reaction speed, thereby reducing the energy consumption and improving the product conversion rate, and ensuring the stable quality of the prepared product.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a process for the preparation of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite comprising the steps of:
(1) Mixing pentaerythritol, phosphorus trichloride, a solvent and a catalyst, and performing a preliminary reaction to obtain an intermediate;
the catalyst comprises a first component: urotropin and a second component: trimethylamine and/or triethylamine;
(2) The intermediate and cumylphenol are mixed for the pre-program temperature and pressure control reaction, then the decompression reaction is carried out, then the solvent is removed and the refining post-treatment is carried out, thus obtaining the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
Preferably, the mass ratio of the first component to the second component is 1 (1-4).
Preferably, the mole ratio of the pentaerythritol, the phosphorus trichloride and the cumylphenol is (1.0-1.05) 2.0 (2.00-2.20).
Preferably, the mass ratio of the catalyst to the cumylphenol is (0.002-0.1): 1.
Preferably, the programmed temperature and pressure control reaction is carried out according to the following conditions:
a.1, heating to 60+/-5 ℃, and keeping the temperature under the condition of normal pressure or micro negative pressure for reacting for 0.5-2 h;
a.2, heating to 80+/-5 ℃, and keeping the temperature under the condition of micro negative pressure for reacting for 20-40 min;
a.3, heating to 120+/-5 ℃, and keeping the temperature under the condition of micro negative pressure for 0.5-2 h;
a.4, heating to 140+/-5 ℃, and keeping the temperature at micro-boiling and micro-negative pressure for reaction for 1.5-3 h;
wherein the micro negative pressure is specifically gauge pressure not exceeding-0.01 Mpa.
Preferably, the temperature of the decompression reaction is 125-135 ℃, the vacuum degree is-0.04 MPa to-0.06 MPa, and the time is 1-3 h.
Preferably, the solvent removal adopts reduced pressure distillation, specifically: treating at 130 ℃ +/-10 ℃ and the vacuum degree of minus 0.06MPa to minus 0.08MPa for 20-30 min, and then treating at 130 ℃ -150 ℃ and the vacuum degree of minus 0.07MPa to minus 0.098 MPa.
Preferably, the post-refining treatment is: the obtained product is dissolved, filtered and the solvent is removed, and then recrystallized.
Further preferably, the post-refining treatment is specifically:
mixing the obtained product with a first solvent, heating to 130-140 ℃, regulating the pH to be more than 12, filtering and removing the solvent, mixing the obtained product with a second solvent, heating to 135-145 ℃, and cooling for crystallization.
Preferably, the first solvent and the second solvent are independently selected from xylene and/or toluene.
In a second aspect, the present invention provides a bis (2, 4-dicumylphenyl) pentaerythritol diphosphite prepared according to the above-described process, having a purity of greater than 99.5%, a melting point of 228.5 to 230.5 ℃, and an acid value of not more than 0.03mgKOH/g.
In a third aspect, the present invention provides an antioxidant for a polymer comprising bis (2, 4-dicumylphenyl) pentaerythritol diphosphite obtained by the above process.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a preparation method of high molecular weight bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, which adopts a mixed catalyst of urotropine, trimethylamine and/or triethylamine as a composite catalyst for early reaction of pentaerythritol and phosphorus trichloride, and compared with the prior art which adopts single triethylamine or amine hydrochloride as a catalyst, the preparation method can achieve high-efficiency synergistic catalysis, can effectively accelerate the reaction speed, better shorten the reaction time, thereby reducing the energy consumption, can control the stable and efficient reaction and further improve the product conversion rate and the product quality by adopting the subsequent reaction of intermediates and cumylphenol, the decompression reaction and the matching of solvent removal and the exquisite post-treatment operation, and has the advantages of high purity (more than 99.5 ℃), low acid value (not more than 0.03 mgKOH/g) of Cheng Zhai (228.5-230.5 ℃) and low melt index, and the obtained bis (2, 4-dicumylphenyl) pentaerythritol diphosphite through research, and the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite has low oxidation index and excellent stability;
(2) In the preparation method, 2, 4-dicumyl phenol (a high molecular weight and high temperature resistant alkylphenol) is adopted as a raw material, so that the preparation method is safer, healthier and environment-friendly compared with the 2, 4-di-tert-butylphenol commonly used in the prior art;
(3) The solvent used in each step of the preparation method can be recovered and recycled, so that the turnover amount is reduced, and the economic cost is reduced.
Drawings
FIG. 1 is a FTIR spectrum of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite obtained in example 1;
FIG. 2 is a liquid chromatogram of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite obtained in example 1.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Aiming at the problems of immature production technology of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, high energy consumption, low product conversion rate and unstable product quality in the prior art, the invention provides a preparation method of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, which comprises the following steps:
(1) Mixing pentaerythritol, phosphorus trichloride, a solvent and a catalyst, and performing a preliminary reaction to obtain an intermediate;
the catalyst comprises a first component: urotropin and a second component: trimethylamine and/or triethylamine;
(2) The intermediate and cumylphenol are mixed for the pre-program temperature and pressure control reaction, then the decompression reaction is carried out, then the solvent is removed and the refining post-treatment is carried out, thus obtaining the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
According to the invention, pentaerythritol, phosphorus trichloride, a solvent and a catalyst are first mixed and subjected to a preliminary reaction, in which step the hydroxyl groups in pentaerythritol and chlorine atoms in phosphorus trichloride undergo a substitution reaction in the presence of the catalyst to give an intermediate. The sources of pentaerythritol and phosphorus trichloride are not particularly limited, and the pentaerythritol and phosphorus trichloride are common commercial products. In some embodiments of the invention, the solvent is selected from aromatic hydrocarbon solvents, in particular from xylenes and/or toluene, and the catalyst comprises urotropine and trimethylamine and/or triethylamine. In some embodiments of the present invention, it is preferred to first mix pentaerythritol, solvent and catalyst, and then add phosphorus trichloride dropwise to the system to keep the reaction state steady, ultimately yielding an intermediate. In some embodiments of the present invention, it is preferable that the molar ratio of pentaerythritol to phosphorus trichloride is (1.0 to 1.05): 2.0, the amount (volume, liter) of the solvent to be added for the preliminary reaction is about 1 to 1.5 times (mass, kg) that of 2, 4-dicumylphenol, then pentaerythritol, the solvent and the catalyst are mixed, and then phosphorus trichloride is added dropwise to the system to obtain an intermediate after the reaction. The reaction is preferably carried out at normal temperature (25 to 35 ℃). It has been studied that when the mass ratio of the first component to the second component in the catalyst is 1 (1-4), the catalytic synergistic effect is good, and therefore, in some embodiments of the present invention, it is preferable to control the mass ratio of the first component to the second component in the catalyst to be 1 (1-4), specifically 1:1, 1:1.5, 1:2, 1:2.3, 1:2.5, 1:3, 1:3.5, 1:4, or the like.
After the intermediate is obtained, the intermediate and cumylphenol are mixed for a programmed temperature and pressure control reaction to obtain a reaction solution of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite. In some embodiments of the present invention, to ensure that the reaction state is stable, the cumylphenol is preferably added dropwise to a system containing an intermediate in the form of a solution for performing a programmed temperature and pressure control reaction, wherein the solvent used in the cumylphenol solution is an aromatic hydrocarbon solvent, and may be specifically selected from xylene and/or toluene. In some embodiments of the invention, the mass ratio of the catalyst to the cumylphenol is (0.002-0.1): 1, and the cumylphenol solution is dropwise added into a system containing an intermediate for carrying out a programmed temperature and pressure control reaction, wherein the programmed temperature and pressure control reaction is preferably carried out according to the following heating sequence:
a.1, heating to 60+/-5 ℃, and keeping the temperature under the condition of normal pressure or micro negative pressure for reacting for 0.5-2 h;
a.2, heating to 80+/-5 ℃, and keeping the temperature under the condition of micro negative pressure for reacting for 20-40 min;
a.3, heating to 120+/-5 ℃, and keeping the temperature under the condition of micro negative pressure for 0.5-2 h;
a.4, heating to 140+/-5 ℃, and keeping the temperature at micro-boiling and micro-negative pressure for reaction for 1.5-3 h;
wherein the micro negative pressure is specifically gauge pressure not exceeding-0.01 Mpa. The micro-boiling is a reaction state well known to those skilled in the art, and will not be described herein.
In the step a.1, the temperature is preferably controlled to be 5-10 min, the temperature is specifically selected from 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃ or 65 ℃, the temperature may fluctuate during the reaction, but the temperature needs to be controlled within 60+/-5 ℃, and the reaction time is specifically selected from 0.5h, 0.8h, 1h, 1.2h, 1.5h, 1.7h or 2h.
In the step a.2, the heating time is preferably controlled to be 5-10 min, the temperature is specifically selected from 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃ or 85 ℃, the temperature may fluctuate during the reaction, but the temperature needs to be controlled to be within 80+/-5 ℃, and the reaction time is specifically selected from 20min, 25min, 30min, 35min or 40min.
In the step a.3, the heating time is preferably controlled to be 5-10 min, the temperature is specifically selected from 115 ℃, 116 ℃, 117 ℃, 118 ℃, 119 ℃, 120 ℃, 121 ℃, 122 ℃, 123 ℃, 124 ℃ or 125 ℃, the temperature may fluctuate during the reaction, but the reaction time is required to be controlled to be within 120+/-5 ℃, and the reaction time is specifically selected from 0.5h, 0.8h, 1h, 1.2h, 1.5h, 1.7h or 2h.
In the step a.4, the heating time is preferably controlled to be 5-10 min, the temperature is specifically selected from 135 ℃, 136 ℃, 137 ℃, 138 ℃, 139 ℃, 140 ℃, 141 ℃, 142 ℃, 143 ℃, 144 ℃ or 145 ℃, the temperature may fluctuate during the reaction, but the reaction time is required to be controlled to be 140+/-5 ℃, and the reaction time is specifically selected from 1.5h, 1.8h, 2h, 2.2h, 2.5h, 2.7h or 3h. In the steps a.1 to a.4, the temperature is increased in a gradient manner, and the temperature conditions in each step are preferably matched with each other, so that the yield and purity of the product can be further improved.
It should be noted that the values of the temperature and the time are not limited to the values listed, and are not repeated herein as long as they are within the corresponding ranges.
After the completion of the programmed temperature-controlled pressure-controlled reaction, the reaction solution from which bis (2, 4-dicumylphenyl) pentaerythritol diphosphite is obtained is preferably subjected to a reduced pressure reaction in order to further promote the reaction. In some embodiments of the present invention, it is preferable to reflux the reaction solution of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite at a temperature of 125℃to 135℃and a vacuum of-0.04 MPa to-0.06 MPa for 1 to 3 hours.
After the completion of the reduced pressure reaction, the solvent was removed. The removal of the solvent in the present invention is preferably carried out by distillation under reduced pressure, and in some embodiments is specifically divided into two steps, the first step: treating for 20-30 min at 130+/-10 ℃ and the vacuum degree of minus 0.06MPa to minus 0.08 MPa; and a second step of: treating at 130-150 deg.c and vacuum degree of-0.07 MPa to-0.098 MPa, and receiving distilled solvent until no distillate exists. Wherein the distillation temperature in the first step may be 120 ℃, 125 ℃, 130 ℃, 135 ℃ or 140 ℃, and the distillation temperature in the second step may be 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃. Wherein, the temperature is fluctuated during the reaction process, but the temperature is controlled within +/-5 ℃, and the distillation temperature of the second step is preferably higher than that of the first step in the invention, namely, the distillation from the first step to the second step is heating treatment. The solvent obtained by removal can be used for subsequent reaction, can also be directly recovered and used for other reaction solvents, and can effectively reduce economic cost.
After the solvent is removed, a post-refining treatment step is also included to further improve the purity of the product. The refining post-treatment comprises the following steps: the obtained product is dissolved, filtered and the solvent is removed, and then recrystallized. In some embodiments of the invention, the post-refining treatment is specifically: (1) Mixing the obtained product with a first solvent, heating to 130-140 ℃, regulating the pH to be more than 12, and then filtering and removing the solvent; (2) Mixing the obtained product with a second solvent, heating to 135-145 ℃, and then cooling for crystallization. Wherein the first solvent and the second solvent are independently selected from xylene and/or toluene, the process of removing the solvent is referred to the corresponding content in the above technical scheme, and will not be described herein, and the temperature of the cooling crystallization is preferably reduced to below 20 ℃. In the invention, the step (1) is used for dissolving and filtering, is mainly used for removing some impurities which are insoluble in the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, is used for absorbing HCl generated in the previous reaction and the process of the program temperature and pressure control reaction, the step (2) is used for removing some impurities which are slightly soluble in the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite by recrystallization, and the steps (1) and (2) are matched, so that the purity of the product can be further improved. In some embodiments of the present invention, the crystallization after cooling preferably further comprises centrifugation, washing and drying steps, and after the centrifugation, the centrifugation mother liquor may be taken and the solvent may be further distilled for recovery. In some embodiments of the present invention, it is preferred that the solid obtained by centrifugation is washed with an alcoholic solvent, such as isopropanol, and dried to obtain the target product, i.e., bis (2, 4-dicumylphenyl) pentaerythritol diphosphite. The washing mother liquor obtained after washing can also be distilled to recover the alcohol solvent, so that the waste of the solvent is avoided.
The preparation method of the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite provided by the invention adopts the mixture of urotropine and trimethylamine and/or triethylamine as a composite catalyst for the early reaction of pentaerythritol and phosphorus trichloride, and compared with the prior art which adopts single triethylamine or amine hydrochloride and single urotropine or trimethylamine as a catalyst, the preparation method can achieve high-efficiency synergistic catalysis, can effectively accelerate the reaction speed, better shorten the reaction time, reduce the energy consumption, and can control the stable and efficient reaction and further improve the product conversion rate and the product quality through the cooperation of the subsequent reaction of an intermediate and cumylphenol, the decompression reaction, the solvent removal and the fine post-treatment operation. In addition, 2, 4-dicumyl phenol (high temperature resistant hindered phenol) is adopted as a raw material in the method, compared with the 2, 4-di-tert-butylphenol commonly used in the prior art, the method is safer, healthier and environment-friendly, and solvents involved in the preparation method can be recycled, so that the turnover quantity is reduced, and the economic cost is reduced.
Through researches, the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite prepared by the preparation method has stable quality, high purity (more than 99.5%), melting Cheng Zhai (228.5-230.5 ℃) and low acid value (not more than 0.03 mgKOH/g).
The bis (2, 4-dicumylphenyl) pentaerythritol diphosphite can be used as an antioxidant in polymers (such as polypropylene, polycarbonate or polyphenylene sulfide, etc.), and the oxidation resistance of the polymers is effectively improved. The invention is added into polypropylene powder, and the melt index and the yellow index in the three extrusion experiments are low and stable, which shows that the polypropylene powder has excellent oxidation resistance.
In the preparation method, the reaction equation is as follows:
in order to further illustrate the present invention, the following examples are provided. The experimental materials used in the following examples of the present invention are not particularly limited and may be purchased commercially or prepared according to conventional techniques well known to those skilled in the art.
Example 1
This example provides a bis (2, 4-dicumylphenyl) pentaerythritol diphosphite prepared as follows:
(1) Sequentially adding 40.0 kg of pentaerythritol, 300L of dimethylbenzene, 0.2 kg of urotropine and 0.8 kg of trimethylamine into a No. 1 reaction kettle (with the volume of 1500L), dropwise adding 78.0 kg of phosphorus trichloride at normal temperature (25-35 ℃) for about 30 minutes at uniform speed, starting initial reaction, and obtaining a first intermediate after the reaction is completed;
(2) Raising the temperature to about 60 ℃, dropwise adding a cumylphenol xylene solution (containing 800L of xylene and 200 kg of cumylphenol at the temperature of 60 ℃) into the first intermediate, and continuing to react for 1 hour, wherein the dropwise adding is completed; heating to 80 ℃ to keep the reaction for 30 minutes, and slightly negative pressure; raising the temperature to 120 ℃ and keeping the reaction for 1 hour, and carrying out micro negative pressure; heating to 140 ℃ and keeping the reaction for 2 hours, and slightly boiling and slightly negative pressure;
(3) Then, the reaction was carried out under reduced pressure: temperature range: 125-135 deg.c and vacuum degree range: reflux reaction for 2 hours under the pressure of-0.04 MPa to-0.06 MPa; after the reaction is completed, xylene is distilled off, and the temperature is: 130 ℃ +/-10 ℃ and pressure: -0.06MPa to-0.08 MPa for a period of time: 20-30 minutes; and (3) steaming out at the later stage: temperature: 130-150 ℃ and the pressure: steaming at-0.07 MPa to-0.098 MPa until no distillation is carried out basically, and collecting and obtaining 1080L of recovered reaction xylene; adding 1300L of dissolved xylene, stirring fully, stirring to a No. 2 reaction kettle (3000L), washing the reaction kettle and a pipeline twice with 200L of xylene respectively, stirring to the No. 2 reaction kettle, heating to 130-140 ℃ for redissolution, and regulating the pH value to be more than 12; 2.0 kg of diatomite is wetted and mixed with about 15L of xylene, the mixture is added into a reaction kettle, the reaction kettle is filtered circularly, dissolved xylene in the reaction liquid is distilled off until the dissolved xylene is not distilled off basically, and about 1700L of recovered dissolved xylene is collected to obtain a crude product;
(4) Adding 2200L of crystalline dimethylbenzene into the crude product, heating to 135-145 ℃ for dissolution, cooling for crystallization, and cooling to below 20 ℃; after crystallization is completed, centrifugal drying is carried out, centrifugal mother liquor is collected, and crystalline dimethylbenzene is recovered by distillation; washing and spin-drying the product with about 200L of isopropanol after centrifugation, collecting washing mother liquor, distilling and recovering the washing isopropanol, drying and packaging product filter residues to obtain 239 kg of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite with purity: 99.56%, melting point: 228.7-229.9 ℃ and acid value of 0.03mgKOH/g.
Example 2
This example provides a bis (2, 4-dicumylphenyl) pentaerythritol diphosphite prepared as follows:
(1) 39.0 kg of pentaerythritol, 300L of dimethylbenzene, 0.5 kg of urotropine and 0.5 kg of trimethylamine are sequentially added into a No. 1 reaction kettle (with the volume of 1500L), 78.0 kg of phosphorus trichloride is dropwise added at normal temperature (25-35 ℃) for about 30 minutes at uniform speed, initial reaction is started, and a first intermediate is obtained after the reaction is completed;
(2) Raising the temperature to about 60 ℃, dropwise adding cumylphenol xylene solution (containing 750L of xylene and 198 kg of cumylphenol at the temperature of 60 ℃) for continuous reaction, and completing dropwise adding for 1 hour; heating to 80 ℃ to keep the reaction for 30 minutes, and slightly negative pressure; raising the temperature to 120 ℃ and keeping the reaction for 1 hour, and carrying out micro negative pressure; heating to 140 ℃ and keeping the reaction for 2 hours, and slightly boiling and slightly negative pressure;
(3) Then, the reaction was carried out under reduced pressure: temperature range: 125-135 deg.c and vacuum degree range: reflux reaction for 2 hours under the pressure of-0.04 MPa to-0.06 MPa; after the reaction is completed, xylene is distilled off, and the temperature is: 130 ℃ +/-10 ℃ and pressure: -0.06MPa to-0.08 MPa for a period of time: 20-30 minutes; and (3) steaming out at the later stage: temperature: 130-150 ℃ and the pressure: evaporating to almost no distillation under the pressure of-0.07 MPa to-0.098 MPa, and collecting and obtaining 1030L of recovered reaction xylene; adding 1300L of dissolved xylene, stirring fully, stirring to a No. 2 reaction kettle (3000L), washing the reaction kettle and a pipeline twice with 200L of xylene respectively, stirring to the No. 2 reaction kettle, heating to 130-140 ℃ for redissolution, and regulating the pH value to be more than 12; 2.0 kg of diatomite is wetted and mixed with about 15L of xylene, the mixture is added into a reaction kettle, the reaction kettle is filtered circularly, dissolved xylene in the reaction liquid is distilled off until the dissolved xylene is not distilled off basically, and about 1700L of recovered dissolved xylene is collected to obtain a crude product;
(4) Adding 2100L of crystalline dimethylbenzene into the crude product, heating to 135-145 ℃ for dissolution, cooling for crystallization, and cooling to below 20 ℃; after crystallization is completed, centrifugal drying is carried out, centrifugal mother liquor is collected, and crystalline dimethylbenzene is recovered by distillation; washing and spin-drying the finished centrifugation by using about 200L of isopropanol, collecting washing mother liquor, and distilling and recovering the washing isopropanol; the product filter residue is dried and packaged to obtain 238 kg of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite with purity: 99.57%, melting point: 228.8-229.9 ℃ and acid value of 0.03mgKOH/g.
Example 3
This example provides a bis (2, 4-dicumylphenyl) pentaerythritol diphosphite prepared as follows:
(1) 39.0 kg of pentaerythritol, 300L of recovered reaction xylene, 0.3 kg of urotropine and 0.7 kg of trimethylamine are sequentially added into a No. 1 reaction kettle (with the volume of 1500L), 78.0 kg of phosphorus trichloride is dropwise added at normal temperature (25-35 ℃) for about 30 minutes at uniform speed, initial reaction is started, and a first intermediate is obtained after the reaction is completed;
(2) Raising the temperature to about 60 ℃, dropwise adding a cumylphenol xylene solution (containing 700L of recovered reaction xylene and 190 kg of cumylphenol, and the solution temperature being 60 ℃) for continuous reaction, and completing dropwise adding for 1 hour; heating to 80 ℃ to keep the reaction for 30 minutes, and slightly negative pressure; raising the temperature to 120 ℃ and keeping the reaction for 1 hour, and carrying out micro negative pressure; heating to 140 ℃ and keeping the reaction for 2 hours, and slightly boiling and slightly negative pressure;
(3) Then, the reaction was carried out under reduced pressure: temperature range: 125-135 deg.c and vacuum degree range: reflux reaction for 2 hours under the pressure of-0.04 MPa to-0.06 MPa; after the reaction is completed, xylene is distilled off, and the temperature is: 130 ℃ +/-10 ℃ and pressure: -0.06MPa to-0.08 MPa for a period of time: 20-30 minutes; and (3) steaming out at the later stage: temperature: 130-150 ℃ and the pressure: steaming at-0.07 MPa to-0.098 MPa until no distillation is carried out basically, and collecting and obtaining 980L of recovered reaction xylene; adding about 1300L of recovered and dissolved xylene, stirring fully, stirring and stirring to obtain a No. 2 reaction kettle (3000L), respectively using 200L of recovered and dissolved xylene to wash the reaction kettle and a pipeline twice, stirring to obtain a No. 2 reaction kettle, heating to 130-140 ℃ to redissolve, and regulating the pH to be more than 12; 2.0 kg of diatomite is wetted and mixed with about 15L of xylene, the mixture is added into a reaction kettle, the reaction kettle is filtered circularly, dissolved xylene in the reaction liquid is distilled off until the dissolved xylene is not distilled off basically, and about 1700L of recovered dissolved xylene is collected to obtain a crude product;
(4) Adding 2200L of recovered crystalline dimethylbenzene into the crude product, heating to 135-145 ℃ for dissolution, cooling for crystallization, and cooling to below 20 ℃; after crystallization is completed, centrifugal drying is carried out, centrifugal mother liquor is collected, and crystalline dimethylbenzene is recovered by distillation; washing and spin-drying with about 200L of recovered isopropanol after centrifugation, collecting washing mother liquor, and distilling to recover the washed isopropanol; the product filter residue is dried and then packaged to obtain 235 kg of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite with purity: 99.63%, melting point: 229.2-230.2 ℃ and acid value of 0.03mgKOH/g.
Comparative example 1
This comparative example provides a bis (2, 4-dicumylphenyl) pentaerythritol diphosphite prepared as follows:
(1) Sequentially adding 38.0 g of pentaerythritol, 300 ml of toluene and 1.0 g of urotropine into a 2000 ml four-port glass flask, dropwise adding 78.0 g of phosphorus trichloride at normal temperature (25-35 ℃) for about 30 minutes, starting an initial reaction, and obtaining a first intermediate after the reaction is completed;
(2) Raising the temperature to about 60 ℃, dropwise adding a cumylphenol toluene solution (containing 750 ml of toluene and 190 g of cumylphenol at the temperature of 60 ℃) into the first intermediate, and continuing to react for 1 hour, wherein the dropwise adding is completed; heating to 80 ℃ to keep the reaction for 30 minutes, and slightly negative pressure; heating to 110 ℃ and keeping the reaction for 1 hour, and carrying out micro negative pressure; heating to 120 ℃ and keeping the reaction for 2 hours, and slightly boiling and slightly negative pressure;
(3) Then, the reaction was carried out under reduced pressure: temperature range: 105-115 ℃ and vacuum degree range: reflux reaction for 2 hours under the pressure of-0.04 MPa to-0.06 MPa; toluene was distilled off after the reaction was completed, and the temperature: 110 ℃ +/-10 ℃ and pressure: -0.06MPa to-0.08 MPa for a period of time: 20-30 minutes; and (3) steaming out at the later stage: temperature: 110-130 ℃, pressure: evaporating to almost no distillation under the pressure of-0.07 MPa to-0.098 MPa, and collecting 1030 milliliters of recovered reaction toluene; adding about 1300 ml of dissolved toluene, fully stirring, transferring to a 5000 ml glass flask, washing the original 2000 ml glass flask with 400 ml of toluene, transferring to the 5000 ml flask, heating to 110-120 ℃ for redissolution, and regulating the pH to be more than 12; 2.0 g of kieselguhr is moistened and mixed with about 15 ml of toluene, the mixture is added into a flask and filtered, the filtrate is recycled to the original 5000 ml glass flask, the dissolved toluene in the filtrate is distilled off, and the distillation is not carried out basically, so that a crude product is obtained;
(4) 2100 ml of crystalline toluene is added into the crude product, the temperature is raised to 115 ℃ to 125 ℃ for dissolution, then the temperature is lowered to below 20 ℃ for crystallization; after crystallization is completed, vacuum filtration is carried out; washing with about 200 ml of isopropanol after the suction filtration is finished, and suction filtration; the filter residue of the product is dried and packaged to obtain 187 g of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite with purity: 96.29%, melting point: 221.0-227.8 deg.C and acid value of 0.39mgKOH/g.
Comparative example 2
This comparative example provides a bis (2, 4-dicumylphenyl) pentaerythritol diphosphite prepared as follows:
(1) 41.0 g of pentaerythritol, 300 ml of toluene and 1.0 g of trimethylamine are sequentially added into a 2000 ml four-necked glass flask, 78.0 g of phosphorus trichloride is dropwise added at normal temperature (25-35 ℃) for about 30 minutes, and initial reaction is started;
(2) After the reaction is finished, the temperature is raised to about 60 ℃, cumylphenol toluene solution (containing 750 ml of toluene and 188 g of cumylphenol, and the solution temperature is 60 ℃) is added dropwise for continuous reaction, and the dropwise addition is finished for 1 hour; heating to 80 ℃ to keep the reaction for 30 minutes, and slightly negative pressure; heating to 110 ℃ and keeping the reaction for 1 hour, and carrying out micro negative pressure; heating to 120 ℃ and keeping the reaction for 2 hours, and slightly boiling and slightly negative pressure;
(3) Decompression reaction: temperature range: 105-115 ℃ and vacuum degree range: reflux reaction for 2 hours under the pressure of-0.04 MPa to-0.06 MPa; toluene was distilled off after the reaction was completed, and the temperature: 110 ℃ +/-10 ℃ and pressure: -0.06MPa to-0.08 MPa for a period of time: 20-30 minutes; and (3) steaming out at the later stage: temperature: 110-130 ℃, pressure: -0.07MPa to-0.098 MPa, and steaming until no distillation is carried out basically; adding about 1300 ml of dissolved toluene, fully stirring, transferring to a 5000 ml glass flask, washing the original 2000 ml glass flask with 400 ml of toluene, transferring to the 5000 ml flask, heating to 110-120 ℃ for redissolution, and regulating the pH to be more than 12; wetting and mixing 3.0 g of diatomite with about 15 ml of toluene, adding the mixture into a flask, filtering, recycling filtrate to an original 5000 ml glass flask, evaporating the dissolved toluene in the filtrate until the toluene is not distilled out basically, and obtaining a crude product;
(4) 2100 ml of crystalline toluene is added into the crude product, the temperature is raised to 115 ℃ to 125 ℃ for dissolution, then the temperature is lowered to below 20 ℃ for crystallization; after crystallization is completed, vacuum filtration is carried out; washing with about 200 ml of isopropanol after the suction filtration is finished, and suction filtration; the product filter residue is dried and packaged to obtain 188 g of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite with purity: 99.14%, melting point: 227.9-229.4 deg.C and acid value of 0.27mgKOH/g.
Test of antioxidant Properties
0.5 g of the sample obtained in example 2 is weighed and added into 500 g of polypropylene powder (brand PPH 040, comprising basic stabilization system: containing 0.15 g of antioxidant 1010 and 0.25 g of calcium stearate) to be fully and uniformly mixed, and the mixture is extruded three times in an SHJ-20 twin-screw extruder, wherein the screw temperature is set as TS1:265 ℃, TS2:280 ℃, TS3-TS9:285 ℃, TS10:260 ℃. The melt index, yellowness index of each extruded pellet was sampled and tested and compared to a control, and the test data are shown in tables 1 and 2 below:
TABLE 1
| Foundation stabilization | Comparative example 2 | Example 2 | |
| One-time extrusion | 26.8 | 9.3 | 8.3 |
| Secondary extrusion | 51.4 | 16.5 | 11.8 |
| Three times of extrusion | 70.7 | 41.6 | 13.4 |
TABLE 2
| Foundation stabilization | Comparative example 2 | Example 2 | |
| One-time extrusion | 0.15 | -1.2 | -1.4 |
| Secondary extrusion | 2.64 | 0.91 | 0.49 |
| Three times of extrusion | 4.72 | 2.93 | 1.08 |
As can be seen from the data in tables 1 and 2, the product of example 2 of the present invention can significantly stabilize the melt index change process during the multiple processing processes, and improve the color stability of the product.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for preparing bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, which is characterized by comprising the following steps:
(1) Mixing pentaerythritol, phosphorus trichloride, a solvent and a catalyst, and performing a preliminary reaction to obtain an intermediate;
the catalyst comprises a first component: urotropin and a second component: trimethylamine and/or triethylamine;
(2) The intermediate and cumylphenol are mixed for the pre-program temperature and pressure control reaction, then the decompression reaction is carried out, then the solvent is removed and the refining post-treatment is carried out, thus obtaining the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
2. The preparation method according to claim 1, wherein the mass ratio of the first component to the second component is 1 (1-4);
the mole ratio of the pentaerythritol, the phosphorus trichloride and the cumylphenol is (1.0-1.05) 2.0 (2.00-2.20);
the mass ratio of the catalyst to the cumylphenol is (0.002-0.1): 1.
3. The preparation method according to claim 1, wherein the programmed temperature and pressure control reaction is performed under the following conditions:
a.1, heating to 60+/-5 ℃, and keeping the temperature under the condition of normal pressure or micro negative pressure for reacting for 0.5-2 h;
a.2, heating to 80+/-5 ℃, and keeping the temperature under the condition of micro negative pressure for reacting for 20-40 min;
a.3, heating to 120+/-5 ℃, and keeping the temperature under the condition of micro negative pressure for 0.5-2 h;
a.4, heating to 140+/-5 ℃, and keeping the temperature at micro-boiling and micro-negative pressure for reaction for 1.5-3 h;
wherein the micro negative pressure is specifically gauge pressure not exceeding-0.01 Mpa.
4. The preparation method according to claim 1, wherein the reduced pressure reaction is carried out at a temperature of 125-135 ℃ and a vacuum degree of-0.04 to-0.06 MPa for 1-3 hours.
5. The preparation method according to claim 1, wherein the solvent removal is performed by distillation under reduced pressure, specifically: treating at 130 ℃ +/-10 ℃ and the vacuum degree of minus 0.06MPa to minus 0.08MPa for 20-30 min, and then treating at 130 ℃ -150 ℃ and the vacuum degree of minus 0.07MPa to minus 0.098 MPa.
6. The method according to claim 1, wherein the post-refining treatment is: the obtained product is dissolved, filtered and the solvent is removed, and then recrystallized.
7. The method according to claim 6, wherein the post-refining treatment is specifically:
mixing the obtained product with a first solvent, heating to 130-140 ℃, regulating the pH to be more than 12, filtering and removing the solvent, mixing the obtained product with a second solvent, heating to 135-145 ℃, and cooling for crystallization.
8. The method of claim 7, wherein the first solvent and the second solvent are independently selected from xylenes and/or toluene.
9. The bis (2, 4-dicumylphenyl) pentaerythritol diphosphite produced by the process according to any one of claims 1 to 8, wherein the purity is greater than 99.5%, the melting point is 228.5 to 230.5 ℃, and the acid value is not more than 0.03mgKOH/g.
10. An antioxidant for a polymer comprising bis (2, 4-dicumylphenyl) pentaerythritol diphosphite according to claim 9.
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