CN113372187B - 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 '-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 synthetic route, and particularly relates to an industrial synthetic 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, so that the use application of the p-chlorostyrene is limited.
An improved synthesis route of BVPE is reported in Russian Journal of Applied Chemistry (2011), 84 (10), 1783-1794, namely BVPE of 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 chemical structure to BVPE. Patent document WO0023485 discloses a synthesis method of BVPM, which adopts PTSA and TBC to react for 1.5-2 h, wherein the crude reaction yield is 88-91.9%, the main peak GC content is 79-87%, and the dimer GC content 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, 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;
s2, under the action of sodium borohydride, 4 '-diacetyl diaryl ethane reacts in a solvent to obtain 4,4' - (1, 2-ethyl dialkyl) bis (alpha-methyl benzyl alcohol);
and (3) reacting S3 and 4,4' - (1, 2-ethyl dialkyl) bis (alpha-methyl benzyl alcohol) with p-toluenesulfonic acid by selecting polymerization inhibitor p-tert-butyl catechol and phenothiazine to obtain the BVPE.
Preferably, the reaction conditions of step S1: the reaction solvent is dichloromethane or dichloroethane, the reaction temperature is 0-40 ℃, the reaction time is 1-3h, the molar ratio of 1, 2-diphenylethane to aluminum trichloride to acetyl chloride is 1.1-2.5.
Further preferably, the 4,4 '-diacetyl diaryl ethane prepared in the step S1 needs to be purified to obtain a pure product, wherein a purifying solvent of the 4,4' -diacetyl diaryl ethane is toluene or dichloroethane, and the mass ratio of the purifying solvent to the 1, 2-diphenyl ethane is 6-12.
Preferably, the reaction conditions of step S2 are: the molar ratio of the 4,4 '-diacetyl diaryl ethane to the sodium borohydride is 1.8-1.2, the reaction solvent is 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, the reaction temperature is 20 ℃ to the reflux temperature of the reaction solvent, and the reaction time is 2-4 h.
Preferably, the reaction conditions of step S3 are: the mol ratio of 4,4' - (1, 2-ethyldialkyl) bis (alpha-methylbenzyl alcohol) to p-toluenesulfonic acid, p-tert-butylcatechol and phenothiazine is 1.
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 inhibitor, so that the polymerization inhibition capability is improved, the GC content of the main peak can reach 96% after the reaction is finished, and the content of the dimer is about 2%, so that the polymerization of the product is effectively avoided, and the purification cost of the crude 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 requirement on equipment is 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 the example of the present invention 1 H-NMR chart.
FIG. 2 shows BVPE prepared in example of the present invention 13 C-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 synthesis of the intermediate 4,4' -diacetyldiarylethane, or specific synthetic steps.
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 added dropwise, 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 added dropwise, the temperature is increased to 40 ℃ after the addition is finished, and the reflux reaction is carried out for 1h. After the reaction was detected by GC (gas chromatography), methylene chloride was extracted and concentrated to obtain a crude product, 2187.6g of toluene was added to the crude product to recrystallize (purify) the crude product to obtain 243.5g of a refined product, the GC content of which was 98.8%, and the yield of which was 90.1%.
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 ℃, a mixed solution of 182.3g of 4-acetyl phenol and 1276.1g of dichloromethane is dripped, and the reaction is kept at the temperature of 0 ℃ 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 to obtain a refined product 243.0g, the GC content is 98.9 percent, and the yield is 89.9 percent.
Synthesis of intermediate 4,4' - (1, 2-ethyldialkyl) bis (alpha-methylbenzyl alcohol)
This example gives an exemplary operating specification, or specific synthetic steps, for the synthesis of the intermediate 4,4' - (1, 2-ethyldialkyl) bis (. Alpha. -methylbenzyl alcohol).
Example 1
243g of 4,4' -diacetyldiarylethane is mixed with 1215g of ethanol and 243g of water, stirred at room temperature, 41.4g of sodium borohydride are added, and the reaction is carried out under reflux for 2h. 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 246.7 g) of wet 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 are mixed, stirred at room temperature, 27.6g of sodium borohydride are added and reacted at 20 ℃ for 2h. After the reaction is finished by GC detection, pouring the reaction liquid into a hydrochloric acid aqueous solution, filtering, leaching a filter cake with water to obtain 285g (the theoretical amount is 246.7 g) of the wet weight of the product, and directly using the product in the next reaction without purification. The product has a GC content of 98.4% and a yield of 100%.
Synthesis of the BVPE of the invention
This example gives an exemplary operating specification, or specific synthesis steps, for BVPE synthesis according to the present invention.
Example 1
285g of 4,4' - (1, 2-ethyldialkyl) bis (alpha-methylbenzyl alcohol) (246.7 g of theoretical amount) and 3700g of toluene are mixed and stirred, the reflux flow is heated and divided until no water is distilled off, the temperature is reduced to 30 to 40 ℃, 7.8g of p-toluenesulfonic acid, 0.3g of TBC and 0.4g of phenothiazine are added, and the temperature is raised, the reflux flow is divided and reacted 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
285g of 4,4' - (1, 2-ethyldialkyl) bis (alpha-methylbenzyl alcohol) (246.7 g of theoretical amount) and 2280g of dimethylbenzene are mixed and stirred, reflux water is distributed when no water is distilled out after heating, the temperature is reduced to 30-40 ℃, 1.6g of p-toluenesulfonic acid, 1.5g of TBC and 1.8g of phenothiazine are added, and reflux water distribution reaction is carried out for 1 hour after heating. 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 invention 1 FIG. 1 shows H-NMR. As can be seen from fig. 1, the nuclear magnetic spectrum data are: 1 H-NMR(600MHz,CDCl 3 ,δppm)，7.31-7.33(m，4H)，7.11-7.13(m，4H),6.66-6.71(m,2H),5.69-5.72(dd,J 1 ＝1.2HZ,J 2 ＝17.4HZ,2H),5.18-5.20(dd,J 1 ＝1.2HZ,J 2 =10.8hz, 2h), 2.89 (s, 4H), consistent with literature reports.
Of the BVPE of the present invention 13 The C-NMR chart is shown in FIG. 2. As can be seen from fig. 2, the nuclear magnetic spectrum data are: 13 C-NMR(151MHz,CDCl 3 ,δppm), 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.
285g of 4,4' - (1, 2-ethyldialkyl) bis (alpha-methylbenzyl alcohol) (246.7 g of theoretical amount) and 2280g of dimethylbenzene are mixed and stirred, reflux and water separation are carried out while heating until no water is distilled off, the temperature is reduced to 30-40 ℃, 1.6g of p-toluenesulfonic acid and 1.5g of TBC are added, and reflux and water separation are carried out while heating 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 various 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 (4)
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:
s1, 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 '-diacetyl diaryl ethane reacts in a solvent to obtain 4,4' - (1, 2-ethyl dialkyl) bis (alpha-methyl benzyl alcohol);
s3, 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 BVPE;
the reaction conditions of the step S1: the reaction solvent is dichloromethane or dichloroethane, the reaction temperature is 0-40 ℃, the reaction time is 1-3h, the molar ratio of the 1, 2-diphenylethane to the aluminum trichloride to the acetyl chloride is 1.1-2.5, 2.2-2.7, and the mass ratio of the reaction solvent to the 1, 2-diphenylethane is 8-14.
2. The industrial synthesis method of BVPE according to claim 1, wherein the purifying solvent of 4,4' -diacetyl diaryl ethane is toluene or dichloroethane, and the mass ratio of the purifying solvent to 1, 2-diphenylethane is 6-12.
3. The industrial synthesis method of BVPE according to claim 1, characterized in that the reaction conditions of step S2 are: the mol ratio of the 4,4 '-diacetyl diaryl ethane to the sodium borohydride is 1.8-1.2, the reaction solvent is any one or the mixture of two solvents of ethanol, methanol and water, the mass ratio of the reaction solvent to the 4,4' -diacetyl diaryl ethane is 6-8, the reaction temperature is 20 ℃ to the reflux temperature of the reaction solvent, and the reaction time is 2-4 h.
4. The industrial synthesis method of BVPE according to claim 1, characterized in that the reaction conditions of step S3: the mol ratio of 4,4' - (1, 2-ethyldialkyl) bis (alpha-methylbenzyl alcohol) to p-toluenesulfonic acid, p-tert-butylcatechol and phenothiazine is 1.
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