Preparation method for bvpe
By using pyridine to modify the acidic environment during BVPE synthesis, the problems of high raw material cost and low yield were solved, achieving the preparation of high-purity, high-yield BVPE, which is suitable for industrial applications.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- PLUS SCI TECH (SHANGHAI) CO LTD
- Filing Date
- 2025-01-15
- Publication Date
- 2026-07-09
AI Technical Summary
Existing BVPE synthesis methods suffer from high raw material costs or low yields, making it difficult to meet the needs of industrial production. Furthermore, olefin polymerization severely affects purity.
By using pyridine as a catalyst to change the acidic environment of the reaction system, combined with p-toluenesulfonic acid and chlorobenzene solvent, BVPE is prepared through a dehydration reaction, which reduces olefin polymerization and improves yield and purity.
This method achieves high-yield and high-purity BVPE synthesis, reduces production costs, and is suitable for industrial production.
Smart Images
Figure CN2025072534_09072026_PF_FP_ABST
Abstract
Description
A method for preparing BVPE TECHNICAL FIELD
[0001] The present application relates to the field of organic synthesis, in particular to a method for preparing BVPE. BACKGROUND
[0002] BVPE (P, P'-divinyl-1, 2-diphenyl ethane) is a widely used olefin monomer, and its annual demand is increasing rapidly at home and abroad.
[0003] Currently, there are two main synthetic routes for synthesizing BVPE.
[0004] Route one is to generate the target product BVPE by Grignard coupling reaction of p-chloromethylstyrene and magnesium powder under specific conditions. This method has the advantages of fast reaction and high yield, and the polymerization reaction is relatively less, which helps to maintain the purity of the product. The disadvantage is that the price of p-chloromethylstyrene is high, which increases the production cost and has no advantage in industrial production.
[0005] Route two is to generate BVPE by dehydration of 4, 4'-(1, 2-ethanediy) bis (alpha methylbenzene alcohol) under the action of an acidic catalyst. Although the raw material cost of this route is relatively low, the polymerization is very serious due to the acidic catalysis, and the yield is generally low, which is difficult to meet the demand of large-scale production. SUMMARY
[0006] In view of the above-mentioned deficiencies in the synthesis of BVPE, the present application provides a method for preparing BVPE, which introduces pyridine to change the acidic environment of the reaction system and synthesize BVPE by dehydration. Through experimental optimization, the polymerization of olefins is effectively reduced, and high-yield BVPE synthesis is achieved. This method is suitable for industrial production because the raw materials are easy to obtain and the cost is controllable.
[0007] To achieve the above purpose, the embodiments of the present application adopt the following technical solutions:
[0008] A method for preparing BVPE, the method comprising dehydrating 4, 4'-(1, 2-ethanediy) bis (alpha methylbenzene alcohol) in the presence of a reaction material to generate BVPE; the reaction material comprises a pyridine-based catalyst, a p-toluenesulfonic acid-based catalyst, and a chlorobenzene-based solvent.
[0009] Preferably, the pyridine-based catalyst comprises pyridine, collidine and tetramethylpyridine; and the chlorobenzene-based solvent comprises chlorobenzene, dimethylbenzene and trimethylbenzene.
[0010] Preferably, chlorobenzene is used at 30-60 times the weight of toluenesulfonic acid and pyridine at 0.424-0.623 times the weight of p-toluenesulfonic acid, and more preferably, 1 part by weight of p-toluenesulfonic acid, 40 parts by weight of chlorobenzene and 0.5 parts by weight of pyridine are used.
[0011] Preferably, the preparation method includes mixing p-toluenesulfonic acid, chlorobenzene, and pyridine to obtain a mixed catalyst, adding 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol), and carrying out a dehydration reaction to obtain BVPE.
[0012] In this application, 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol) undergoes the removal of two water molecules in chlorobenzene under the catalysis of p-toluenesulfonic acid to generate BVPE. Because BVPE contains two olefin structures, it readily undergoes polymerization under acidic conditions, generating various polymers, making it difficult to obtain pure BVPE. By adding pyridine, a weakly alkaline environment is provided in the solvent, significantly reducing the repolymerization of BVPE and achieving a high yield of BVPE.
[0013] Preferably, the preparation of the mixed catalyst by mixing p-toluenesulfonic acid, chlorobenzene, and pyridine comprises: heating the mixture of p-toluenesulfonic acid, chlorobenzene, and pyridine at a temperature of 35-45°C; at this temperature, sufficient reflux can be achieved, promoting a stable start and progress of the hydrolysis reaction, avoiding increased time loss due to excessively low heating rates, and increased side reactions due to excessively rapid heating rates. The dehydration reaction to obtain BVPE comprises: heating under reflux after adding 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol) for 2.5-3.5 hours, separating the layers, and distilling the upper layer under reduced pressure to obtain BVPE.
[0014] Preferably, the heating reflux reaction includes the following steps: heating and refluxing a mixed catalyst containing 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol), separating the generated water, detecting the raw material content to a preset value, cooling and adding water, stirring and then letting it stand.
[0015] Preferably, the temperature of the heating reflux reaction is 130-135℃; the raw material content detection is set to a preset value of less than 1%.
[0016] Preferably, the vacuum distillation includes the following steps: subjecting a mixed catalyst containing 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol) to vacuum distillation to recover chlorobenzene, cooling and adding methanol, stirring and centrifuging to separate the solid, and drying the solid.
[0017] Preferably, the conditions for recovering chlorobenzene under reduced pressure are collecting the fraction at 78-92 DEG C under a pressure of 5.4-6.0 kPa; the temperature for adding methanol is 28-32 DEG C, the stirring time is 50-70 min, and the centrifugation temperature is 13-17 DEG C.
[0018] In another aspect, a synthesis method for preparing BVPE from 1,2-diphenylethane, comprising the following steps:
[0019] S1, using 1,2-diphenylethane as raw material, reacting in a solvent under the action of aluminum chloride and acetyl chloride to obtain 4,4'-diacetyldiaryl ethane;
[0020] S2, 4,4'-diacetyldiaryl ethane reacts in a solvent under the action of sodium borohydride to obtain 4,4'-(1,2-ethylenediamine) bis(alpha-methyl benzyl alcohol);
[0021] S3, p-toluenesulfonic acid, chlorobenzene, and pyridine are mixed and heated, 4,4'-(1,2-ethylenediamine) bis(alpha-methyl benzyl alcohol) is added to obtain a raw material mixture, heated to reflux for 2.5-3.5 hours, separated, and the upper layer is distilled under reduced pressure to obtain BVPE.
[0022] The advantages of the embodiment of the present application are: by introducing pyridine to change the acidic environment of the reaction system, the polymerization of olefins is effectively reduced, and the yield and purity of BVPE are improved. In addition, the raw materials of the present application are relatively easy to obtain, and the production cost is greatly reduced, which further enhances the industrial application potential of the method, making large-scale production of BVPE possible. BRIEF DESCRIPTION OF DRAWINGS
[0023] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.
[0024] Figure 1 is a H-NMR chart of BVPE prepared in the embodiment of the present application. 1 H-NMR chart. DETAILED DESCRIPTION
[0025] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Test methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions or according to the conditions recommended by the respective manufacturers.
[0026] Material source
[0027] p-Toluenesulfonic acid is available from Jinan Renyuan Chemical Co., Ltd.
[0028] Chlorobenzene is available from Jiangsu Longchang Chemical Co., Ltd.
[0029] Pyridine is available from Shandong Kunda Biotechnology Co., Ltd.
[0030] 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol) is available from Xi'an Tuochao Biotechnology Co., Ltd.
[0031] Example 1
[0032] BVPE was prepared using the following method according to this application:
[0033] 15 kg of p-toluenesulfonic acid, 600 kg of chlorobenzene, and 7.5 kg of pyridine were mixed evenly and heated to 40°C. The mixture was stirred for 30 minutes, and then 100 kg of 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol) was added. The mixture was heated under reflux for 3 hours, and the water generated was separated during the reaction. The raw material content was checked and found to be less than 1%. The mixture was cooled to 20°C, and 200 kg of water was added. The mixture was stirred for 30 minutes, and the organic phase was separated by standing. The mixture was washed once with water, and most of the chlorobenzene was recovered under reduced pressure below 80°C. After the chlorobenzene was recovered, the mixture was cooled to 30°C, and 300 kg of methanol was added. The mixture was stirred for 1 hour, cooled to 15°C, centrifuged, and dried to obtain 70 kg of product (purity 99.68%; yield 80.8%).
[0034] Example 2
[0035] BVPE was prepared using the following method according to this application:
[0036] 15 kg of p-toluenesulfonic acid, 600 kg of chlorobenzene, and 7.5 kg of pyridine were mixed evenly and heated to 38°C. The mixture was stirred for 28 minutes, and then 100 kg of 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol) was added. The mixture was heated under reflux for 3 hours, and the water generated was separated during the reaction. The raw material content was found to be less than 1%. The mixture was cooled to 20°C, and 200 kg of water was added. The mixture was stirred for 30 minutes, allowed to stand, and the organic phase was separated. The mixture was washed once with water, and most of the chlorobenzene was recovered under reduced pressure below 80°C. After the chlorobenzene was recovered, the mixture was cooled to 30°C, and 300 kg of methanol was added. The mixture was stirred for 1 hour, cooled to 15°C, centrifuged, and dried to obtain 69.3 kg of product (purity 99.66%; yield 80%).
[0037] Example 3
[0038] BVPE was prepared using the following method according to this application:
[0039] 15 kg of p-toluenesulfonic acid, 600 kg of chlorobenzene, and 7.5 kg of pyridine were mixed evenly and heated to 40°C. The mixture was stirred for 30 minutes, and then 100 kg of 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol) was added. The mixture was heated under reflux for 2.5 hours, and the water generated was separated during the reaction. The raw material content was found to be less than 1%. The mixture was cooled to 20°C, and 200 kg of water was added. The mixture was stirred for 30 minutes, and the organic phase was separated by standing. The mixture was washed once with water, and most of the chlorobenzene was recovered under reduced pressure below 80°C. After the chlorobenzene was recovered, the mixture was cooled to 30°C, and 300 kg of methanol was added. The mixture was stirred for 1 hour, cooled to 15°C, centrifuged, and dried to obtain 66.9 kg of product (purity 99.48%; yield 77.2%).
[0040] Example 4
[0041] BVPE was prepared using the following method according to this application:
[0042] 15 kg of p-toluenesulfonic acid, 600 kg of chlorobenzene, and 7.5 kg of pyridine were mixed evenly and heated to 40°C. The mixture was stirred for 30 minutes, and then 100 kg of 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol) was added. The mixture was heated under reflux for 3 hours, and the water generated was separated during the reaction. The raw material content was found to be less than 2%. The mixture was cooled to 20°C, and 200 kg of water was added. The mixture was stirred for 30 minutes, and the organic phase was separated by standing. The mixture was washed once with water, and most of the chlorobenzene was recovered under reduced pressure below 80°C. After the chlorobenzene was recovered, the mixture was cooled to 30°C, and 300 kg of methanol was added. The mixture was stirred for 1 hour, cooled to 15°C, centrifuged, and dried to obtain 68.5 kg of product (purity 99.55%; yield 79.1%).
[0043] Example 5
[0044] BVPE was prepared using the following method according to this application:
[0045] 15 kg of p-toluenesulfonic acid, 450 kg of chlorobenzene, and 6.36 kg of pyridine were mixed evenly and heated to 40°C. The mixture was stirred for 30 minutes. 100 kg of 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol) was added, and the mixture was heated under reflux for 3 hours. Water generated during the reaction was separated. The raw material content was found to be less than 2%. The mixture was cooled to 20°C, and 200 kg of water was added. The mixture was stirred for 30 minutes, allowed to stand, and the organic phase was separated. The mixture was washed once with water, and most of the chlorobenzene was recovered under reduced pressure below 80°C. After the chlorobenzene was recovered, the mixture was cooled to 30°C, and 300 kg of methanol was added. The mixture was stirred for 1 hour, cooled to 15°C, centrifuged, and dried to obtain 60.8 kg of product (purity 99.3%; yield 70.2%).
[0046] Example 6
[0047] BVPE was prepared using the following method according to this application:
[0048] 15 kg of p-toluenesulfonic acid, 900 kg of chlorobenzene, and 0.623 kg of pyridine were mixed evenly and heated to 40°C. The mixture was stirred for 30 minutes. 100 kg of 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol) was added, and the mixture was heated under reflux for 3 hours. Water generated during the reaction was separated. The raw material content was found to be less than 2%. The mixture was cooled to 20°C, and 200 kg of water was added. The mixture was stirred for 30 minutes, allowed to stand, and the organic phase was separated. The mixture was washed once with water, and most of the chlorobenzene was recovered under reduced pressure below 80°C. After the chlorobenzene was recovered, the mixture was cooled to 30°C, and 300 kg of methanol was added. The mixture was stirred for 1 hour, cooled to 15°C, centrifuged, and dried to obtain 70.2 kg of product (purity 99.61%; yield 81.1%).
[0049] Comparative Example 1
[0050] Except for the reaction using 15 kg of p-toluenesulfonic acid, 300 kg of chlorobenzene, 3 kg of pyridine and 100 kg of 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol), 42.1 kg of BVPE (purity 99.25%; yield 48.6%) was prepared in the same manner as in Example 1.
[0051] Comparative Example 2
[0052] Except for the reaction using 15 kg of p-toluenesulfonic acid, 1000 kg of chlorobenzene, 15 kg of pyridine and 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol), 68.7 kg of BVPE (purity 99.51%; yield 79.3%) was prepared in the same manner as in Example 1.
[0053] Comparative Example 3
[0054] Except that pyridine was not added for the reaction, 10.2 kg of BVPE (purity 95.04%; yield 11.8%) was prepared in the same manner as in Example 1.
[0055] As can be seen from Examples 1 to 6 and Comparative Examples 1 to 3 above, the preparation methods within the scope of this application all yielded BVPE with very high purity and yield. The reaction conditions were mild, reducing olefin polymerization and achieving high-yield synthesis of BVPE. This invention provides a simple and feasible method for synthesizing BVPE.
[0056] Compared with Examples 1-6, Comparative Examples 1-2 used material ratios outside the scope of this application, resulting in a significant decrease in the yield of BVPE. Comparative Example 3 did not add pyridine, which significantly affected the yield of BVPE and also significantly affected the purity of BVPE.
[0057] The advantages of this invention are: by introducing pyridine to change the acidic environment of the reaction system, the polymerization of olefins is effectively reduced, thereby improving the yield and purity of BVPE. Furthermore, the raw materials used in this application are relatively readily available, and production costs are significantly reduced, which further enhances the industrial application potential of this method and makes large-scale production of BVPE possible.
[0058] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.
Claims
1. A method for preparing BVPE, characterized in that, The method comprises dehydrating 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol) to generate BVPE in the presence of reaction materials, wherein the reaction materials include pyridine-based catalysts, p-toluenesulfonic acid-based catalysts, and chlorobenzene-based solvents.
2. The preparation method according to claim 1, characterized in that, The pyridine-based catalysts include pyridine, trimethylpyridine, and tetramethylpyridine; the chlorobenzene-based solvents include chlorobenzene, xylene, and trimethylbenzene.
3. The preparation method according to claim 1, characterized in that, The mixture uses chlorobenzene at a weight of 30-60 times that of toluenesulfonic acid and pyridine at a weight of 0.424-0.623 times that of p-toluenesulfonic acid, preferably 1 part by weight of p-toluenesulfonic acid, 40 parts by weight of chlorobenzene and 0.5 parts by weight of pyridine.
4. The preparation method according to claim 1, characterized in that, The preparation method includes mixing p-toluenesulfonic acid, chlorobenzene, and pyridine to obtain a mixed catalyst, adding 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol), and carrying out a dehydration reaction to obtain BVPE.
5. The preparation method according to claim 4, characterized in that, The preparation of the mixed catalyst by mixing p-toluenesulfonic acid, chlorobenzene, and pyridine includes: heating the mixture of p-toluenesulfonic acid, chlorobenzene, and pyridine at a temperature of 35-45°C; the dehydration reaction to obtain BVPE includes: adding 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol) and then heating under reflux for 2.5-3.5 hours, separating the liquids, and distilling the upper layer under reduced pressure to obtain BVPE.
6. The preparation method according to claim 5, characterized in that, The heating and reflux reaction includes the following steps: a mixed catalyst containing 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol) is heated and refluxed, the generated water is separated, the raw material content is detected to reach a preset value, then the temperature is lowered and water is added, stirred and allowed to stand.
7. The preparation method according to claim 6, characterized in that, The temperature of the heating reflux reaction is 130-135℃; the raw material content is detected to a preset value of less than 1%.
8. The preparation method according to claim 5, characterized in that, The vacuum distillation The process includes the following steps: chlorobenzene is recovered under reduced pressure from a mixed catalyst containing 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol), methanol is added after cooling, the solid is separated by centrifugation after stirring, and the solid is dried.
9. The preparation method according to claim 8, characterized in that, The conditions for the reduced pressure recovery of chlorobenzene are: collecting the fraction at 78-92℃ under a pressure of 5.4-6.0 kPa; the temperature at which methanol is added for cooling is 28-32℃; the stirring time is 50-70 min; and the centrifugation temperature is 13-17℃.
10. A method for synthesizing BVPE using 1,2-diphenylethane as a raw material, characterized in that, Includes the following steps: S1, using 1,2-diphenylethane as a raw material, reacts in a solvent with aluminum trichloride and acetyl chloride to yield 4,4'-diacetyldiarylethane; S2, under the action of sodium borohydride, 4,4'-diacetyldiarylethane reacts in a solvent to give 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol); S3, p-toluenesulfonic acid, chlorobenzene, and pyridine are mixed evenly and heated, and 4,4'-(1,2-ethylenedialkyl)bis(α-methylbenzyl alcohol) is added to obtain a raw material mixture. The mixture is heated under reflux for 2.5-3.5 hours, separated, and the upper layer is distilled under reduced pressure to obtain BVPE.