Supported stannous chloride catalyst as well as preparation method and application thereof
The preparation of a supported stannous chloride catalyst has solved the problems of environmental pollution and resource waste in the production of pentaerythritol stearate, achieving efficient and environmentally friendly catalytic reaction and product recovery, and reducing production costs.
Patent Information
- Application Number
- CN202511550791.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-28
- Publication Date
- 2026-02-10
AI Technical Summary
Existing catalysts for the production of pentaerythritol stearate pose environmental pollution and resource waste problems, making it difficult to achieve efficient and environmentally friendly catalytic reactions and product recovery.
A supported stannous chloride catalyst was prepared by mixing stannous chloride, polyethylene, and clay to form a highly active and recyclable catalyst for the esterification reaction of pentaerythritol stearate.
This method enables the production of pentaerythritol stearate with high yield and high purity, avoids wastewater generation, reduces production costs, and supports multiple recycling of the catalyst.
Smart Images
Figure CN121490790A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of catalyst technology, and in particular to a supported stannous chloride catalyst, its preparation method, and its application. Background Technology
[0002] Pentaerythrityl tetrastearate (PETS), also known as pentaerythritol stearate, is typically a white, hard, high-melting-point waxy substance. It is non-toxic and soluble in solvents such as ethanol, benzene, and chloroform. It is mainly used as an internal and external lubricant and release agent for polycarbonate, rubber and plastics, alloys, nylon (such as PA66 and PA6), polyphenoxyether (PPO), and polyphenylene sulfide (PPS), as well as a lubricant and dispersant for thermoplastic polyesters (such as PBT and PET). It has broad market application prospects.
[0003] The traditional production process of pentaerythritol stearate involves an esterification reaction of pentaerythritol and stearic acid under high temperature conditions in the presence of a catalyst. Currently, catalysts used in the production of pentaerythritol stearate mainly include p-toluenesulfonic acid, solid acids, and stannous chloride. Among these, the synthesis of pentaerythritol stearate using p-toluenesulfonic acid as a catalyst results in a complete reaction and good yield, but requires water washing to remove the p-toluenesulfonic acid after the reaction, leading to the generation of large amounts of acidic wastewater, increasing environmental pressure, and the p-toluenesulfonic acid cannot be recycled. The synthesis of pentaerythritol stearate using solid acids as catalysts has a slightly longer reaction time, a yellowish reaction solution, and some solid acid produces fine debris during the reaction, affecting product quality, and the reaction generates solid hazardous waste. The synthesis of pentaerythritol stearate using stannous chloride as a catalyst results in a faster reaction and a lighter-colored reaction solution, but stannous chloride dissolves in it, generating large amounts of stannous chloride wastewater that is difficult to recover and reuse.
[0004] Therefore, developing a novel, environmentally friendly, recyclable catalyst is a pressing technical problem that needs to be solved in this field. Summary of the Invention
[0005] This invention provides a supported stannous chloride catalyst, which features high catalytic activity and environmental friendliness. It can be recycled and reused, greatly reducing production costs. Using this supported stannous chloride catalyst to prepare pentaerythritol stearate, the obtained pentaerythritol stearate has high yield and high purity, and the preparation process does not generate wastewater containing stannous chloride, making it environmentally friendly. The supported stannous chloride catalyst can be recycled and reused, resulting in low production costs.
[0006] The present invention also provides a method for preparing a supported stannous chloride catalyst. The supported stannous chloride catalyst can be prepared by the method. The supported stannous chloride catalyst has the characteristics of high catalytic activity and environmental friendliness. It can be recycled and reused, effectively reducing the production cost of pentaerythritol stearate. The preparation method is simple and can be widely used.
[0007] This invention also provides a method for preparing pentaerythritol stearate, which uses the above-mentioned supported stannous chloride catalyst to prepare pentaerythritol stearate. The obtained pentaerythritol stearate has high yield and high purity, and the preparation process does not generate wastewater containing stannous chloride, which is environmentally friendly. The supported stannous chloride catalyst can be recycled and reused, and the production cost is low.
[0008] The first aspect of the present invention provides a supported stannous chloride catalyst, wherein the raw materials for preparing the supported stannous chloride catalyst include, by weight, 1.5-2.5 parts of stannous chloride, 8-12 parts of polyethylene, and 0.5-1.0 parts of clay.
[0009] The supported stannous chloride catalyst described above has a stannous chloride loading of 10wt%-20wt%.
[0010] The supported stannous chloride catalyst described above, wherein the polyethylene is high-density polyethylene, and the melt index of the high-density polyethylene is 8-20 g / 10 min under the conditions of 190°C and 21.6 kg;
[0011] And / or, the clay includes kaolin.
[0012] A second aspect of the present invention provides a method for preparing the supported stannous chloride catalyst, comprising:
[0013] Stannous chloride, polyethylene, clay, and ethanol were mixed, heated under nitrogen atmosphere and refluxed, cooled and filtered, the solid product was collected, washed, dried, calcined at high temperature, and sieved to obtain the supported stannous chloride catalyst.
[0014] In the preparation method of the supported stannous chloride catalyst described above, 5-15 mL of ethanol needs to be added for every 1 g of polyethylene added.
[0015] In the preparation method of the supported stannous chloride catalyst as described above, the drying temperature is 45-55℃ and the time is 5-7h;
[0016] And / or, the high-temperature calcination temperature is 250-300℃ and the time is 4-6h.
[0017] In the preparation method of the supported stannous chloride catalyst described above, the sieving is performed through a 50-100 mesh sieve.
[0018] A third aspect of the present invention provides a method for preparing pentaerythritol stearate, comprising the following steps:
[0019] Pentaerythritol, stearic acid, and supported stannous chloride catalyst were subjected to esterification reaction at 200-260℃ for 2-10h, and then cooled to 120-130℃ for hot filtration. The filtrate and the supported stannous chloride catalyst were collected separately. The collected filtrate was decolorized to obtain pentaerythritol stearate.
[0020] The supported stannous chloride catalyst is the above-mentioned supported stannous chloride catalyst or the supported stannous chloride catalyst prepared by the above-mentioned preparation method.
[0021] In the method for preparing pentaerythritol stearate as described above, the mass of stannous chloride in the supported stannous chloride catalyst is 0.3%-1% of the total mass of pentaerythritol and stearic acid.
[0022] The method for preparing pentaerythritol stearate as described above involves collecting the supported stannous chloride catalyst, heating it under nitrogen protection in xylene under reflux, filtering, washing, and vacuum drying before recycling.
[0023] The supported stannous chloride catalyst provided by this invention is prepared from raw materials including stannous chloride, polyethylene, and clay. This supported stannous chloride catalyst features high catalytic activity and environmental friendliness, and can be recycled, significantly reducing production costs. Using this supported stannous chloride catalyst to prepare pentaerythritol stearate yields high-quality pentaerythritol stearate with high purity, and the preparation process does not generate stannous chloride-containing wastewater, making it environmentally friendly. The supported stannous chloride catalyst is recyclable, resulting in low production costs. The preparation method of this supported stannous chloride catalyst is simple and can be widely applied. Furthermore, compared with traditional stannous chloride catalysts, the recovery process of this supported stannous chloride catalyst is simple, allowing for multiple recycling without wastewater generation. The resulting pentaerythritol stearate product has a high yield, reducing production costs and improving economic efficiency. Attached Figure Description
[0024] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0025] Figure 1 This is a photograph of the calcined catalyst in Example 1 of the present invention. Detailed Implementation
[0026] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention. Unless otherwise specified, the raw materials and reagents used in the following embodiments are commercially available; the processes used, unless otherwise specified, are conventional processes in the art.
[0027] In the following description, the term "and / or" is used to describe the relationship between related objects, indicating that there can be three relationships. For example, A and / or B can mean: A exists alone, B exists alone, and A and B exist simultaneously. A and B can be singular or plural.
[0028] Those skilled in the art should understand that, in the following description of the present invention, the sequence of numbers does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present invention.
[0029] Those skilled in the art will understand that the numerical ranges in this invention should be understood to specifically disclose each intermediate value between the upper and lower limits of the range. Each smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included within this application. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.
[0030] Unless otherwise stated, the technical / scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. While only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.
[0031] The first aspect of the present invention provides a supported stannous chloride catalyst, wherein the raw materials for preparing the supported stannous chloride catalyst include, by weight, 1.5-2.5 parts of stannous chloride, 8-12 parts of polyethylene, and 0.5-1.0 parts of clay.
[0032] Specifically, the supported stannous chloride catalyst of the present invention is prepared from raw materials including stannous chloride, polyethylene, and clay. This supported stannous chloride catalyst has the characteristics of high catalytic activity and environmental friendliness, and can be recycled, greatly reducing production costs. Using this supported stannous chloride catalyst to prepare pentaerythritol stearate, the obtained pentaerythritol stearate has high yield and high purity, and the preparation process does not generate wastewater containing stannous chloride, which is environmentally friendly. The supported stannous chloride catalyst can be recycled and reused, resulting in low production costs. The preparation method of this supported stannous chloride catalyst is simple and can be widely promoted and applied.
[0033] In this invention, polyethylene plays a supporting role, and clay plays a binding role. The polyethylene and clay in this invention are matched with stannous chloride, which increases the mechanical strength of the supported stannous chloride catalyst while preventing the supported stannous chloride catalyst from breaking into powder during use, thus increasing the difficulty of filtration and recovery.
[0034] To achieve a proper balance between polyethylene, clay, and stannous chloride, and to avoid excessive stannous chloride existing in a free state and to prevent the resulting product from having low mechanical strength, the following proportions are used: 1.5-2.5 parts by weight of stannous chloride, 8-12 parts by weight of polyethylene, and 0.5-1.0 parts by weight of clay.
[0035] In one specific embodiment, the stannous chloride loading in the supported stannous chloride catalyst is 10wt%-20wt%.
[0036] When the stannous chloride loading in the supported stannous chloride catalyst is within the above range, the prepared supported stannous chloride catalyst has the advantage of high catalytic activity. Using this supported stannous chloride catalyst, pentaerythritol stearate with high yield and high purity can be prepared, improving the selectivity of the target product. If the stannous chloride loading in the supported stannous chloride catalyst is too low, it may lead to insufficient activity; if the stannous chloride loading in the supported stannous chloride catalyst is too high, it is easy to cause particle aggregation and reduce the specific surface area.
[0037] In one specific embodiment, the polyethylene is high-density polyethylene, and the melt index of the high-density polyethylene is 8-20 g / 10 min under the conditions of 190°C and 21.6 kg.
[0038] When the polyethylene used is the aforementioned high-density polyethylene, it is beneficial to prepare a supported stannous chloride catalyst with high catalytic activity and certain mechanical strength.
[0039] In one specific embodiment, the clay includes kaolin.
[0040] When the clay used is the aforementioned material, it is beneficial to obtain a supported stannous chloride catalyst with stronger adhesion and less brittleness, which facilitates filtration and recovery.
[0041] A second aspect of the present invention provides a method for preparing the supported stannous chloride catalyst, comprising: mixing stannous chloride, polyethylene, clay, and ethanol; heating under reflux in a nitrogen atmosphere; cooling and filtering; collecting the solid product; washing; drying; high-temperature calcination; and sieving to obtain the supported stannous chloride catalyst. The preparation process of the supported stannous chloride catalyst is carried out under a nitrogen atmosphere to prevent oxygen in the air from damaging the catalyst; sieving is to select a supported stannous chloride catalyst of suitable size. If the particle size of the supported stannous chloride catalyst is too large, the catalytic effect will be weakened; if the particle size of the supported stannous chloride catalyst is too small, it may increase the difficulty of filtration and recovery.
[0042] In one specific implementation, 5-15 mL of ethanol needs to be added for every 1 g of polyethylene added.
[0043] In one specific embodiment, the drying temperature is 45-55°C and the time is 5-7 hours.
[0044] In one specific embodiment, the high-temperature calcination temperature is 250-300℃ and the time is 4-6h.
[0045] When the temperature and time parameters of the high-temperature calcination mentioned above are each within the above range, it is beneficial to obtain a supported stannous chloride catalyst with a high stannous chloride loading.
[0046] In one specific embodiment, the sieving is performed through a 50-100 mesh sieve.
[0047] When the particle size of the supported stannous chloride catalyst is 50-100 mesh, using it as a catalyst in the preparation of pentaerythritol stearate can accelerate the reaction and improve the yield and purity of the obtained pentaerythritol stearate.
[0048] A third aspect of the present invention provides a method for preparing pentaerythritol stearate, comprising the following steps:
[0049] Pentaerythritol, stearic acid, and a supported stannous chloride catalyst were subjected to an esterification reaction at 200-260°C for 2-10 hours. The mixture was then cooled to 120-130°C and subjected to hot filtration. The filtrate and the supported stannous chloride catalyst were collected separately. The collected filtrate was decolorized to obtain pentaerythritol stearate. The supported stannous chloride catalyst was either the above-mentioned supported stannous chloride catalyst or a supported stannous chloride catalyst prepared by the above-mentioned preparation method.
[0050] In this invention, if the heat filtration temperature is below 100°C, the viscosity of pentaerythritol stearate will gradually increase as the temperature decreases; if the heat filtration temperature is below 60°C, pentaerythritol stearate will solidify. The preferred heat filtration temperature is 120-130°C to prevent pentaerythritol stearate from cooling and solidifying during the filtration process.
[0051] This invention uses the above-mentioned supported stannous chloride catalyst to prepare pentaerythritol stearate. The obtained pentaerythritol stearate has high yield and high purity, and the preparation process does not generate wastewater containing stannous chloride, which is environmentally friendly. The supported stannous chloride catalyst can be recycled and reused, and the production cost is low.
[0052] In one specific embodiment, to obtain pentaerythritol stearate with high yield and high purity, the mass of stannous chloride in the supported stannous chloride catalyst is 0.3%-1% of the total mass of pentaerythritol and stearic acid. If the mass of stannous chloride in the supported stannous chloride catalyst is too small, the synthesis reaction of pentaerythritol stearate will be slow, and the target product pentaerythritol tetrastearate (with all four hydroxyl groups of pentaerythritol esterified) will decrease as the amount of catalyst decreases in the same time. If the mass of stannous chloride in the supported stannous chloride catalyst is too large, it will waste the catalyst and cause pentaerythritol stearate dimer impurities to appear during the reaction.
[0053] In one specific embodiment, the collected supported stannous chloride catalyst is heated and refluxed in xylene under nitrogen protection, filtered, washed, and vacuum dried before being recycled and reused. This indicates that the recovery process of the supported stannous chloride catalyst is simple, and the recovered supported stannous chloride catalyst can be recycled multiple times without generating wastewater, effectively reducing the preparation cost of pentaerythritol stearate.
[0054] The present invention will be further described below through specific embodiments.
[0055] In the following examples, stannous chloride was purchased from Innoca, catalog number A23596; high-density polyethylene was purchased from Aladdin, catalog number P434350-1kg, with a melt index of 12g / 10min at 190℃ and 21.6kg; clay was purchased from Innoca, catalog number A00315, specifically kaolin; p-toluenesulfonic acid was purchased from Aladdin, catalog number T684184-100G; solid acid catalyst was purchased from Hubei Maidehao Chemical Co., Ltd.; purity was determined by gel permeation chromatography.
[0056] Example 1
[0057] In this embodiment, supported stannous chloride is prepared through the following process:
[0058] 1.5 g of stannous chloride, 8 g of high-density polyethylene, 0.5 g of clay, and 50 mL of ethanol were added to a four-necked flask and heated under reflux for 5 h in a nitrogen atmosphere. After cooling to room temperature, the mixture was filtered, and the solid product was collected. The solid product was washed with ethanol, dried in a vacuum drying oven at 50 °C for 6 h, and then calcined in a muffle furnace (nitrogen atmosphere, 250 °C) for 5 h to obtain the calcined catalyst. The calcined catalyst was passed through a 50-mesh sieve, and the upper solid was collected to obtain the supported stannous chloride catalyst. The tin content in the supported stannous chloride catalyst was determined by inductively coupled plasma atomic emission spectrometry (ICP), and the stannous chloride loading in the supported stannous chloride catalyst was determined to be 13.5 wt%.
[0059] Example 2
[0060] In this embodiment, supported stannous chloride is prepared through the following process:
[0061] 2g of stannous chloride, 12g of high-density polyethylene, 1g of clay, and 150mL of ethanol were added to a four-necked flask and heated under reflux for 5 hours in a nitrogen atmosphere. After cooling to room temperature, the mixture was filtered, and the solid product was collected. The solid product was washed with ethanol, dried in a vacuum drying oven at 50℃ for 6 hours, and then calcined in a muffle furnace (nitrogen atmosphere, 280℃) for 5 hours to obtain the calcined catalyst. The calcined catalyst was passed through a 100-mesh sieve, and the upper solid was collected to obtain the supported stannous chloride catalyst. The tin content in the supported stannous chloride catalyst was determined by inductively coupled plasma atomic emission spectrometry (ICP), and the stannous chloride loading in the supported stannous chloride catalyst was determined to be 12.4wt%.
[0062] Example 3
[0063] In this embodiment, supported stannous chloride is prepared through the following process:
[0064] 2.5 g of stannous chloride, 10 g of high-density polyethylene, 0.8 g of clay, and 100 mL of ethanol were added to a four-necked flask and heated under reflux for 5 h in a nitrogen atmosphere. After cooling to room temperature, the mixture was filtered, and the solid product was collected. The solid product was washed with ethanol, dried in a vacuum drying oven at 50 °C for 6 h, and then calcined in a muffle furnace (nitrogen atmosphere, 280 °C) for 5 h to obtain the calcined catalyst. The calcined catalyst was passed through a 100-mesh sieve, and the upper solid was collected to obtain the supported stannous chloride catalyst. The tin content in the supported stannous chloride catalyst was determined by inductively coupled plasma atomic emission spectrometry (ICP), and the stannous chloride loading in the supported stannous chloride catalyst was determined to be 18 wt%.
[0065] Comparative Example 1
[0066] This comparative example provides stannous chloride that has not undergone any treatment.
[0067] Comparative Example 2
[0068] This comparative example provides p-toluenesulfonic acid that has not undergone any treatment.
[0069] Comparative Example 3
[0070] This comparative example provides a solid acid catalyst that has not undergone any treatment.
[0071] Application Example 1
[0072] This application example provides a method for preparing pentaerythritol stearate, comprising the following steps:
[0073] (1) 7g pentaerythritol, 55.2g stearic acid and 1.84g of the supported stannous chloride catalyst in Example 1 (the loading of stannous chloride is 13.5wt%) were added to a four-necked flask. After high vacuum was applied, the esterification reaction was carried out at 220℃ for 9h. The reaction was stopped after passing the control detection by gel permeation chromatography (GPC). The temperature was lowered to 130℃ for hot filtration. The filtrate and the supported stannous chloride catalyst were collected separately.
[0074] (2) The collected filtrate was decolorized to obtain 56.5g of pentaerythritol stearate (PETS). The yield of pentaerythritol stearate was 95.6% and the purity was 98.7%.
[0075] Application Example 2
[0076] This application example provides a method for preparing pentaerythritol stearate, comprising the following steps:
[0077] (1) 7g pentaerythritol, 57.8g stearic acid and 2.38g of the supported stannous chloride catalyst in Example 2 (the loading of stannous chloride is 12.4wt%) were added to a four-necked flask. After high vacuum was applied, the esterification reaction was carried out at 240℃ for 6h. The reaction was stopped after passing the control detection by gel permeation chromatography (GPC). The temperature was lowered to 130℃ for hot filtration. The filtrate and the supported stannous chloride catalyst were collected separately.
[0078] (2) The collected filtrate was decolorized to obtain 57.6g of pentaerythritol stearate (PETS), with a yield of 96% and a purity of 97.2%.
[0079] Application Example 3
[0080] This application example provides a method for preparing pentaerythritol stearate, comprising the following steps:
[0081] (1) 7g pentaerythritol, 57.8g stearic acid and 4.74g of the supported stannous chloride catalyst in Example 2 (the loading of stannous chloride is 12.4wt%) were added to a four-necked flask. After high vacuum was applied, the esterification reaction was carried out at 240℃ for 6h. The reaction was stopped after passing the control detection by gel permeation chromatography (GPC). The temperature was lowered to 130℃ for hot filtration. The filtrate and the supported stannous chloride catalyst were collected separately.
[0082] (2) The collected filtrate was decolorized to obtain 57g of pentaerythritol stearate (PETS). The yield of pentaerythritol stearate was 96.1% and the purity was 98.3%.
[0083] Application Example 4
[0084] This application example provides a method for preparing pentaerythritol stearate, comprising the following steps:
[0085] (1) 7g pentaerythritol, 58.6g stearic acid and 2.19g of the supported stannous chloride catalyst in Example 3 (stannous chloride loading was 18wt%) were added to a four-necked flask. After high vacuum was applied, the esterification reaction was carried out at 220℃ for 7h. The reaction was stopped after passing the control detection by gel permeation chromatography (GPC). The temperature was lowered to 120℃ for hot filtration. The filtrate and the supported stannous chloride catalyst were collected separately.
[0086] (2) The collected filtrate was decolorized to obtain 56.6g of pentaerythritol stearate (PETS). The yield of pentaerythritol stearate was 96% and the purity was 99%.
[0087] Application Example 5
[0088] This application example provides a method for preparing pentaerythritol stearate, comprising the following steps:
[0089] (1) Add 35g pentaerythritol, 275.8g stearic acid and 6.91g of the supported stannous chloride catalyst (stannous chloride loading of 18wt%) from Example 3 into a four-necked flask, evacuate to high vacuum and carry out esterification reaction at 240℃ for 5h. After passing the control detection by gel permeation chromatography (GPC), stop the reaction, cool down to 120℃ and perform hot filtration, and collect the filtrate and the supported stannous chloride catalyst respectively.
[0090] (2) The collected filtrate was decolorized to obtain 286g of pentaerythritol stearate (PETS). The yield of pentaerythritol stearate was 96.5% and the purity was 99%.
[0091] The supported stannous chloride catalyst collected in this application example was heated under nitrogen protection, refluxed in xylene, filtered, washed, and vacuum dried to obtain 6.82 g of supported stannous chloride catalyst (stannous chloride loading of 17.8 wt%). The treated supported stannous chloride catalyst was recovered and reused, and the preparation of pentaerythritol stearate was carried out according to the method described above. The number of times the supported stannous chloride catalyst was reused, the amount of each raw material used, and the mass, yield, and purity of the target product pentaerythritol stearate are shown in Table 1.
[0092] Table 1 shows the number of applications, the amount of each raw material used, and the quality, yield, and purity of the target product, pentaerythritol stearate (PETS).
[0093]
[0094] As shown in Table 1, the supported stannous chloride catalyst has good stability. After being recycled and reused 6 times, the yield and purity of pentaerythritol stearate (PETS) can still reach more than 90%, which greatly reduces the production cost.
[0095] Application Example 6
[0096] This application example provides a method for preparing pentaerythritol stearate, comprising the following steps:
[0097] (1) Add 7g pentaerythritol, 58.6g stearic acid and 0.39g stannous chloride from Comparative Example 1 to a four-necked flask, evacuate to a high vacuum and carry out esterification reaction at 220℃ for 7h. After passing the control detection by gel permeation chromatography (GPC), stop the reaction, cool down to 80℃ and wash 3 times with 80℃ hot water, and separate the upper liquid by hot liquid separation.
[0098] (2) The separated upper liquid was decolorized to obtain 54.2g of pentaerythritol stearate (PETS). The yield of pentaerythritol stearate was 91.5% and the purity was 98.5%.
[0099] Application Example 7
[0100] This application example provides a method for preparing pentaerythritol stearate, comprising the following steps:
[0101] (1) Add 7g pentaerythritol, 55.2g stearic acid and 0.62g p-toluenesulfonic acid from Comparative Example 2 to a four-necked flask, and carry out esterification reaction at 220℃ for 7h after high vacuum. The reaction was stopped after passing the control detection by gel permeation chromatography (GPC). After cooling to 90℃, wash three times with 80℃ hot water and separate the upper liquid by hot liquid separation.
[0102] (2) The separated upper liquid was decolorized to obtain 53.7g of pentaerythritol stearate (PETS). The yield of pentaerythritol stearate was 90.4% and the purity was 98.2%.
[0103] Application Example 8
[0104] This application example provides a method for preparing pentaerythritol stearate, comprising the following steps:
[0105] (1) Add 7g pentaerythritol, 57.8g stearic acid and 0.24g solid acid catalyst from Comparative Example 3 into a four-necked flask, evacuate to high vacuum and carry out esterification reaction at 240℃ for 6h. After passing the control detection by gel permeation chromatography (GPC), stop the reaction, cool down to 120℃ for hot filtration and collect the filtrate.
[0106] (2) The collected filtrate was decolorized to obtain 50.5g of pentaerythritol stearate (PETS). The yield of pentaerythritol stearate was 84.2% and the purity was 97.3%.
[0107] Table 2 summarizes the mass, yield, and purity of the target product pentaerythritol stearate in Application Examples 1-4 and Application Examples 6-8 of this invention.
[0108] Table 2. Mass (PETS), yield, and purity of pentaerythritol stearate in various application examples.
[0109]
[0110] As shown in Table 2, the supported stannous chloride catalyst provided in the embodiments of the present invention can produce pentaerythritol stearate with higher quality, yield and purity.
[0111] In summary, the supported stannous chloride catalyst prepared in the embodiments of the present invention has the characteristics of high catalytic activity (high yield and purity of the target product obtained using the catalyst) and environmental friendliness (no wastewater generated), and can be recycled, greatly reducing production costs. Using this supported stannous chloride catalyst to prepare pentaerythritol stearate yields pentaerythritol stearate with high yield and high purity, and the preparation process does not generate stannous chloride-containing wastewater, making it environmentally friendly. The supported stannous chloride catalyst can be recycled and reused, resulting in low production costs. The preparation method of this supported stannous chloride catalyst is simple and can be widely applied.
[0112] 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 supported stannous chloride catalyst, characterized in that, The raw materials for preparing the supported stannous chloride catalyst include, by weight, 1.5-2.5 parts stannous chloride, 8-12 parts polyethylene, and 0.5-1.0 parts clay.
2. The supported stannous chloride catalyst according to claim 1, characterized in that, The stannous chloride loading in the supported stannous chloride catalyst is 10wt%-20wt%.
3. The supported stannous chloride catalyst according to claim 1, characterized in that, The polyethylene is high-density polyethylene, and the melt index of the high-density polyethylene is 8-20 g / 10 min under the conditions of 190℃ and 21.6 kg. And / or, the clay includes kaolin.
4. A method for preparing the supported stannous chloride catalyst according to any one of claims 1-3, characterized in that, include: Stannous chloride, polyethylene, clay, and ethanol were mixed, heated under nitrogen atmosphere and refluxed, cooled and filtered, the solid product was collected, washed, dried, calcined at high temperature, and sieved to obtain the supported stannous chloride catalyst.
5. The method for preparing the supported stannous chloride catalyst according to claim 4, characterized in that, For every 1g of polyethylene added, 5-15mL of ethanol needs to be added.
6. The method for preparing the supported stannous chloride catalyst according to claim 4, characterized in that, The drying temperature is 45-55℃ and the time is 5-7 hours; And / or, the high-temperature calcination temperature is 250-300℃ and the time is 4-6h.
7. The method for preparing the supported stannous chloride catalyst according to claim 4, characterized in that, The sieving process involves passing the material through a 50-100 mesh sieve.
8. A method for preparing pentaerythritol stearate, characterized in that, Includes the following steps: Pentaerythritol, stearic acid, and supported stannous chloride catalyst were subjected to esterification reaction at 200-260℃ for 2-10h, and then cooled to 120-130℃ for hot filtration. The filtrate and the supported stannous chloride catalyst were collected separately. The collected filtrate was decolorized to obtain pentaerythritol stearate. The supported stannous chloride catalyst is the supported stannous chloride catalyst according to any one of claims 1-3 or the supported stannous chloride catalyst prepared by the preparation method according to any one of claims 4-7.
9. The method for preparing pentaerythritol stearate according to claim 8, characterized in that, The mass of stannous chloride in the supported stannous chloride catalyst is 0.3%-1% of the total mass of pentaerythritol and stearic acid.
10. The method for preparing pentaerythritol stearate according to claim 8, characterized in that, The collected supported stannous chloride catalyst was heated under nitrogen protection in xylene, refluxed, filtered, washed, and vacuum dried before being recycled.