CN113372187A - Industrial synthesis method of BVPE - Google Patents
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Abstract
The invention provides an industrial synthesis method of BVPE. The method specifically comprises the following steps: 1, 2-diphenylethane is taken as a raw material, and reacts in a solvent under the action of aluminum trichloride and acetyl chloride to obtain 4,4' -diacetyl diaryl ethane; under the action of sodium borohydride, 4,4 '-diacetyl diaryl ethane reacts in a solvent to obtain 4,4' - (1, 2-ethyl dialkyl) bis (alpha-methyl benzyl alcohol); 4,4' - (1, 2-ethyl dialkyl) bis (alpha-methyl benzyl alcohol) reacts with p-toluenesulfonic acid by selecting polymerization inhibitor p-tert-butyl catechol and phenothiazine to obtain the BVPE. The preparation method has the advantages of simple preparation process, mild reaction conditions, high product yield and low cost of raw materials, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, relates to optimization and improvement of an olefin monomer synthesis route, and particularly relates to an industrial synthesis method of BVPE.
Background
BVPE (P, P' -divinyl-1, 2-diphenylethane) is a versatile olefin monomer that has applications in various types of polymers. For example, BVPE can be used as a raw material for preparing polypropylene films, can be used to improve the performance of polyphenylene ether resins or other resins, and can be prepared into a chromatographic column for analysis by high performance liquid chromatography.
At present, the conventional preparation method of BVPE is to synthesize the BVPE by taking p-chlorostyrene as a raw material under the action of magnesium powder, copper powder or iron powder. The main technical defects of the method are that the raw material p-chlorostyrene is expensive and the industrialization cost is high, thereby limiting the use application of the p-chlorostyrene.
An improved synthesis route of BVPE is reported in Russian Journal of Applied Chemistry (2011),84(10),1783-1794, namely BVPE as a target product is obtained by taking 1, 2-diphenylethane as a starting material and carrying out Friedel-crafts acylation, Raney nickel high-pressure hydrogenation and p-toluenesulfonic acid dehydration 3 steps. In the synthesis path, ethanol is used as the purification solvent in the step 1, but 27 times of the purification solvent is required to be added, and the usage amount of the solvent is large; the hydrogenation pressure of the step 2 is set to be 7.7Mpa, special hydrogenation equipment is needed, and the requirement on equipment conditions is severe; in the step 3, p-toluenesulfonic acid (PTSA) is dehydrated, because a styrene compound is very easy to polymerize in an acid environment, p-tert-butylcatechol (TBC) is selected as a polymerization inhibitor in the literature, and the reaction process is controlled by controlling the concentration of PTSA, adding PTSA in batches at high and low temperatures and controlling the reaction time. The yield of the target product BVPE fine product in the step 3 is only 55%, the comprehensive yield of the literature is only 44.4%, the cost of the synthesis route is high, and the popularization and the application of the synthesis route are limited.
BVPM (P, P' -divinyl-1, 2-diphenylmethane) is another olefin monomer with a similar compound structure to BVPE. WO0023485 discloses a synthesis method of BVPM, which comprises the steps of carrying out combined reaction on PTSA and TBC for 1.5-2 h, wherein the yield of a crude reaction product is 88-91.9%, the GC content of a main peak is 79-87%, and the GC content of a dimer is 10.5-16.5%. The technical scheme of the patent has the defects that the polymer is large, sublimation equipment is also needed for final purification of the product, industrialization is difficult to realize, and the purification yield is not mentioned.
Disclosure of Invention
Aiming at the technical defects of the conventional synthesis process and route of the BVPE, the invention aims to creatively provide a new synthesis idea for industrial preparation of the BVPE.
Specifically, the invention provides an industrial synthesis method of BVPE, which is characterized in that the BVPE is synthesized by taking 1, 2-diphenylethane as a raw material through three steps of reactions, and the synthetic route is as follows:
based on the synthetic route, the invention provides a preferable BVPE synthetic route suitable for industrial production:
the method specifically comprises the following steps of S1-S3:
s1, 1, 2-diphenylethane is used as a raw material and reacts in a solvent under the action of aluminum trichloride and acetyl chloride to obtain 4,4' -diacetyl diaryl ethane;
s2, under the action of sodium borohydride, 4,4 '-diacetyl diaryl ethane reacts in a solvent to obtain 4,4' - (1, 2-ethyl dialkyl) bis (alpha-methyl benzyl alcohol);
and (2) reacting S3 and 4,4' - (1, 2-ethyl dialkyl) bis (alpha-methyl benzyl alcohol) under the action of p-toluenesulfonic acid by selecting polymerization inhibitor p-tert-butyl catechol and phenothiazine to obtain the BVPE.
Preferably, the reaction conditions of step S1 are: the reaction solvent is dichloromethane or dichloroethane, the reaction temperature is 0-40 ℃, the reaction time is 1-3 hours, the molar ratio of the 1, 2-diphenylethane to the aluminum trichloride and the acetyl chloride is 1: 2.1-2.5: 2.2-2.7, and the mass ratio of the reaction solvent to the 1, 2-diphenylethane is 8-14: 1.
Preferably, the 4,4 '-diacetyl diarylethane prepared in step S1 is purified to obtain a pure product, wherein the purifying solvent for 4,4' -diacetyl diarylethane is toluene or dichloroethane, and the mass ratio of the purifying solvent to 1, 2-diphenylethane is 6-12: 1.
Preferably, the reaction conditions of step S2 are: the molar ratio of the 4,4 '-diacetyl diaryl ethane to the sodium borohydride is 1: 0.8-1.2, the reaction solvent is any one or a mixture of two of ethanol, methanol and water, the mass ratio of the reaction solvent to the 4,4' -diacetyl diaryl ethane is 6-8: 1, the reaction temperature is 20 ℃ to the reflux temperature of the reaction solvent, and the reaction time is 2-4 hours.
Preferably, the reaction conditions of step S3 are: the molar ratio of 4,4'- (1, 2-ethyldialkyl) bis (alpha-methylbenzyl alcohol) to p-toluenesulfonic acid, p-tert-butylcatechol and phenothiazine is 1: 0.01-0.05: 0.002-0.01, the reaction solvent is toluene or xylene, the mass ratio of the reaction solvent to 4,4' - (1, 2-ethyldialkyl) bis (alpha-methylbenzyl alcohol) is 8-15: 1, the reaction temperature is the reflux temperature of the reaction solvent, and the reaction time is 1-2 hours.
The BVPE synthesized by the method is identified by a nuclear magnetic spectrum, and the structure of the compound is P, P' -divinyl-1, 2-diphenylethane. The synthesis idea or method has high yield, simple equipment requirement and low raw material cost, and creates conditions for realizing BVPE large-scale production.
In addition, based on the physicochemical properties of the BVPE, the invention also provides a polymer, the preparation raw material of which comprises the BVPE, and the BVPE is synthesized by the method.
Compared with the prior art, the industrial synthesis method of BVPE has the following beneficial effects or advantages:
1) the BVPE has a simple synthetic route, is synthesized by three steps of reactions, simplifies the reaction and purification processes, has a crude product yield of 97 percent, can achieve 99.6 percent of GC content by simply purifying the product through a column, improves the product yield, and has a comprehensive yield of up to 76.5 percent by optimization and improvement, which is 1.72 times that reported in the literature.
2) The BVPE has low synthesis cost. 1, 2-diphenylethane is selected as a raw material, so that the raw material cost is low; TBC and phenothiazine are added to be used as polymerization inhibitors together, so that the polymerization inhibition capability is improved, the GC content of a main peak can reach 96% after the reaction is finished, and the content of a dimer is about 2%, so that the polymerization of the product is effectively avoided, and the purification cost of a crude product of the product is greatly reduced; meanwhile, reaction equipment which requires conditions is abandoned, which is also a favorable factor for reducing the cost.
3) The BVPE synthesis condition is mild and easy to realize. The purification solvent is toluene or dichloroethane, the purification efficiency is high, the high-pressure hydrogenation method in the prior literature is abandoned, and the mild condition reduction is adopted, so that the requirements on equipment are greatly reduced.
In conclusion, the preparation process is simple, the reaction conditions are mild, the product yield is high, the raw material cost is low, and the method is suitable for industrial production.
Drawings
FIG. 1 shows BVPE prepared in example of the present invention1H-NMR chart.
FIG. 2 shows BVPE prepared in example of the present invention13C-NMR chart.
Detailed Description
Specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments. All other examples, which can be obtained by a person skilled in the art without inventive step based on the examples of the present invention, are within the scope of the present invention, and the test methods without specifying the specific conditions in the following examples are generally performed according to the conventional conditions or according to the conditions suggested by the respective manufacturers.
Synthesis of intermediate 4,4' -diacetyldiarylethane
This example gives an exemplary description of the procedure, or specific synthetic steps, for the synthesis of the intermediate 4,4' -diacetyldiarylethane.
Example 1
333.3g of aluminum trichloride and 729.2g of dichloromethane are mixed and stirred, the temperature is reduced to 0 ℃, 212g of acetyl chloride is dripped, the mixture is stirred and reacted for 30min at the temperature of 0 ℃, 182.3g of mixed solution of 4-acetyl phenol and 729.2g of dichloromethane is dripped, the temperature is increased to 40 ℃ after the addition, and the reflux reaction is carried out for 1 h. After the reaction is finished, the reaction is detected by GC (gas chromatography), dichloromethane is extracted and concentrated to obtain a crude product, 2187.6g of toluene is added for recrystallization (purification), and the product refined product 243.5g, the GC content is 98.8 percent and the yield is 90.1 percent.
Example 2
293.3g of aluminum trichloride and 1276.1g of dichloroethane are mixed and stirred, the temperature is reduced to 0 ℃, 180.6g of acetyl chloride is dripped, the mixture is stirred and reacted for 30min at the temperature of 0 ℃, 182.3g of mixed solution of 4-acetyl phenol and 1276.1g of dichloromethane is dripped, and the mixture is kept at the temperature of 0 ℃ for reaction for 3h after the addition. After the reaction is finished by GC detection, dichloroethane is extracted and concentrated to obtain a crude product, 1095.6g of dichloroethane is added for recrystallization, and 243.0g of a refined product, 98.9 percent of GC content and 89.9 percent of yield are obtained.
Synthesis of intermediate 4,4' - (1, 2-ethyldialkyl) bis (alpha-methylbenzyl alcohol)
This example gives an exemplary operating description, or specific synthetic procedure, for the synthesis of intermediate 4,4' - (1, 2-ethyldialkyl) bis (. alpha. -methylbenzyl alcohol).
Example 1
243g of 4,4' -diacetyldiarylethane and 1215g of ethanol are mixed with 243g of water, stirred at room temperature, 41.4g of sodium borohydride are added, and the reaction is refluxed for 2 hours at elevated temperature. After the reaction is finished by GC detection, the reaction solution is poured into a hydrochloric acid aqueous solution, the filtration is carried out, a filter cake (product) is rinsed by water, and 281g (theoretical amount is 246.7g) of wet weight of the product is obtained, and the product is directly used for the next reaction without purification. The product GC content was 98.6% and the yield was 100%.
Example 2
243g of 4,4' -diacetyldiarylethane and 1944g of methanol were mixed, stirred at room temperature, and 27.6g of sodium borohydride was added to react at 20 ℃ for 2 h. After the reaction is finished by GC detection, pouring the reaction liquid into a hydrochloric acid aqueous solution, filtering, and leaching a filter cake with water to obtain 285g (the theoretical amount is 246.7g) of the wet weight of the product, wherein the product is directly used for the next reaction without purification. The product GC content was 98.4% and the yield was 100%.
Synthesis of the BVPE of the invention
This example gives an exemplary operational description, or specific synthesis steps, of BVPE synthesis according to the present invention.
Example 1
Mixing and stirring 285g of 4,4' - (1, 2-ethyl dialkyl) bis (alpha-methyl benzyl alcohol) (246.7 g of theoretical amount) and 3700g of toluene, heating to reflux and divide water until no water is distilled off, cooling to 30-40 ℃, adding 7.8g of p-toluenesulfonic acid, 0.3g of TBC and 0.4g of phenothiazine, heating to reflux and divide water for reaction for 2 hours. After the reaction was completed, GC content was 94% and dimer content was 4%. Extracting with toluene, drying with water, passing through silica gel column, concentrating, and recrystallizing with toluene. 172.3g of white crystal product is obtained, the GC content of the product is 99.6 percent, and the yield is 80.6 percent.
Example 2
Mixing and stirring 285g of 4,4' - (1, 2-ethyl dialkyl) bis (alpha-methyl benzyl alcohol) (246.7 g of theoretical amount) and 2280g of xylene, heating to reflux and divide water until no water is distilled off, cooling to 30-40 ℃, adding 1.6g of p-toluenesulfonic acid, 1.5g of TBC and 1.8g of phenothiazine, heating to reflux and divide water for reaction for 1 hour. After the reaction was detected by GC, the GC content was 96% and the dimer content was 2%. Extracting with xylene, drying with water, passing through silica gel column, concentrating, and recrystallizing with xylene. 181.8g of white crystal product is obtained, the GC content of the product is 99.6 percent, and the yield is 85 percent.
Of the BVPE of the present invention1The H-NMR chart is shown in FIG. 1. As can be seen from fig. 1, the nuclear magnetic spectrum data are:1H-NMR(600MHz,CDCl3,δppm)，7.31-7.33(m，4H)，7.11-7.13(m，4H),6.66-6.71(m,2H),5.69-5.72(dd,J1＝1.2HZ,J2＝17.4HZ,2H),5.18-5.20(dd,J1＝1.2HZ,J210.8HZ,2H),2.89(s,4H), and literature reportsThe tracks are consistent.
Of the BVPE of the present invention13The C-NMR chart is shown in FIG. 2. As can be seen from fig. 2, the nuclear magnetic spectrum data are:13C-NMR(151MHz,CDCl3δ ppm), 141.36,136.62,135.31128.61,126.18,113.02,37.51, consistent with literature reports.
Comparative example for BVPE Synthesis
In order to highlight the technical effect of using TBC and phenothiazine as polymerization inhibitor together, the invention provides a comparative example of BVPE synthesis, and the exemplary operation or specific synthesis steps of BVPE synthesis are basically the same as those of BVPE synthesis example 2.
Mixing and stirring 285g of 4,4' - (1, 2-ethyl dialkyl) bis (alpha-methyl benzyl alcohol) (246.7 g of theoretical amount) and 2280g of xylene, heating to reflux and separate water until no water is distilled off, cooling to 30-40 ℃, adding 1.6g of p-toluenesulfonic acid and 1.5g of TBC, heating to reflux and separate water to react for 1 hour. After the reaction was completed, GC content was 87% and dimer content was 11%. Extracting with xylene, drying with water, passing through silica gel column, and recrystallizing with xylene. 139g of white crystal product is obtained, the GC content of the product is 99.3 percent, and the yield is 65 percent.
As can be seen from the comparative examples, TBC was used as the sole inhibitor, the dimer content increased from 2% to 11% and the BVPE yield decreased from 85% to 65%.
The present invention describes preferred embodiments and effects thereof. Additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The industrial synthesis method of the BVPE is characterized in that the BVPE is synthesized by taking 1, 2-diphenylethane as a raw material through three steps of reactions, and the synthesis route is as follows:
2. the industrial synthesis method of BVPE according to claim 1, wherein the synthetic route comprises steps S1-S3:
s1, 1, 2-diphenylethane is used as a raw material and reacts in a solvent under the action of aluminum trichloride and acetyl chloride to obtain 4,4' -diacetyl diaryl ethane;
s2, under the action of sodium borohydride, 4,4 '-diacetyl diaryl ethane reacts in a solvent to obtain 4,4' - (1, 2-ethyl dialkyl) bis (alpha-methyl benzyl alcohol);
and (2) reacting S3 and 4,4' - (1, 2-ethyl dialkyl) bis (alpha-methyl benzyl alcohol) under the action of p-toluenesulfonic acid by selecting polymerization inhibitor p-tert-butyl catechol and phenothiazine to obtain the BVPE.
3. The industrial synthesis method of BVPE according to claim 2, characterized in that the reaction conditions of step S1 are: the reaction solvent is dichloromethane or dichloroethane, the reaction temperature is 0-40 ℃, the reaction time is 1-3 hours, the molar ratio of the 1, 2-diphenylethane to the aluminum trichloride and the acetyl chloride is 1: 2.1-2.5: 2.2-2.7, and the mass ratio of the reaction solvent to the 1, 2-diphenylethane is 8-14: 1.
4. The industrial synthesis method of BVPE according to claim 3, wherein the purifying solvent of 4,4' -diacetyl diarylethane is toluene or dichloroethane, and the mass ratio of the purifying solvent to 1, 2-diphenylethane is 6-12: 1.
5. The industrial synthesis method of BVPE according to claim 2, characterized in that the reaction conditions of step S2 are: the molar ratio of the 4,4 '-diacetyl diaryl ethane to the sodium borohydride is 1: 0.8-1.2, the reaction solvent is any one or a mixture of two of ethanol, methanol and water, the mass ratio of the reaction solvent to the 4,4' -diacetyl diaryl ethane is 6-8: 1, the reaction temperature is 20 ℃ to the reflux temperature of the reaction solvent, and the reaction time is 2-4 hours.
6. The industrial synthesis method of BVPE according to claim 2, characterized in that the reaction conditions of step S3 are: the molar ratio of 4,4'- (1, 2-ethyldialkyl) bis (alpha-methylbenzyl alcohol) to p-toluenesulfonic acid, p-tert-butylcatechol and phenothiazine is 1: 0.01-0.05: 0.002-0.01, the reaction solvent is toluene or xylene, the mass ratio of the reaction solvent to 4,4' - (1, 2-ethyldialkyl) bis (alpha-methylbenzyl alcohol) is 8-15: 1, the reaction temperature is the reflux temperature of the reaction solvent, and the reaction time is 1-2 hours.
7. BVPE synthesized using the method of any one of claims 1 to 6.
8. A polymer comprising BVPE as a starting material for its preparation, synthesized by the process of any one of claims 1 to 6.
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| CN115385774A (en) * | 2022-08-24 | 2022-11-25 | 上海凌凯医药科技有限公司 | Preparation method of di-sec-aromatic alcohol |
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| 钟世华等: "苯乙烯-双(对乙烯基苯基)乙烷共聚物的超高交联吸附树脂的合成及其对茶碱吸附性能研究", 《湖南师范大学自然科学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115385774A (en) * | 2022-08-24 | 2022-11-25 | 上海凌凯医药科技有限公司 | Preparation method of di-sec-aromatic alcohol |
| CN115385774B (en) * | 2022-08-24 | 2023-08-22 | 上海凌凯医药科技有限公司 | Preparation method of di-secondary aromatic alcohol |
| CN115385767A (en) * | 2022-09-01 | 2022-11-25 | 上海凌凯医药科技有限公司 | Preparation method of divinyl aromatic compound |
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