CN112694380B - Preparation method of 2, 3-dimethyl-2, 3-diphenylbutane - Google Patents

Preparation method of 2, 3-dimethyl-2, 3-diphenylbutane Download PDF

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CN112694380B
CN112694380B CN201911014247.8A CN201911014247A CN112694380B CN 112694380 B CN112694380 B CN 112694380B CN 201911014247 A CN201911014247 A CN 201911014247A CN 112694380 B CN112694380 B CN 112694380B
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reaction
cumene
paraquat
dimethyl
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CN112694380A (en
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汪超
金国杰
杨洪云
丁琳
黄政
康陈军
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention provides a preparation method of 2, 3-dimethyl-2, 3-diphenylbutane, which comprises the following steps: cumene is subjected to a free radical coupling reaction under the action of dicumyl peroxide to give a product stream containing 2, 3-dimethyl-2, 3-diphenylbutane. The invention adopts dicumyl peroxide as the free radical initiator, particularly can realize the recycling of the free radical initiator, can be combined with the CHP-PO process, shares part of reaction units and reduces the investment and the cost.

Description

Preparation method of 2, 3-dimethyl-2, 3-diphenylbutane
Technical Field
The invention relates to the field of preparation of carbon-based free radical initiators, and particularly relates to a preparation method of 2, 3-dimethyl-2, 3-diphenylbutane.
Background
Paraquat, 2, 3-dimethyl-2, 3-diphenylbutane, is a carbon-based radical initiator that forms radicals by dissociation of the C-C bond between quaternary carbons. The paraquat can be used as a modification additive of a polymer material. Compared with the paraquat, the common free radical initiator generally needs to be used at a lower temperature, such as azo compounds, peroxides and the like, the use temperature does not exceed 200 ℃, the decomposition temperature of the paraquat is higher, and the half-life period of the paraquat can still reach 30 minutes at 230 ℃, so that the paraquat can be used for polymer crosslinking or grafting reaction at a high temperature. In addition, the paraquat does not contain oxygen, which is beneficial to improving the oxidation resistance of the processed polymer. At present, the most important application of the paraquat is a synergist in a flame-retardant polymeric material, and the addition of the synergist can obviously improve the oxygen index of the material and shorten the flame extinguishing time.
The preparation of the paraquat can be realized by different routes, one route is that paraquat and zinc chloride are obtained by a condensation reaction of metal organic compounds, such as a compound of dimethylbenzyl chloride and zinc powder, and the method has the main problems that the metal organic compounds are unstable and have high risk, the byproduct metal halide salt is difficult to treat, and the product cost is high.
Another route is that cumene (cumene) can be promoted to form the corresponding isopropylbenzene radical by a radical initiator, and the isopropylbenzene radical can be coupled in pairs to obtain the paraquat. This path is relatively gentle. However, after any kind of free radical initiator completes the initiation task, corresponding byproducts are still generated, the accumulated byproducts in the system need to be effectively separated in order to avoid the influence on the paraquat product, and if no byproduct recycling scheme exists, the production of the paraquat means that the free radical initiator is almost equimolar consumed, and meanwhile, a large amount of byproducts are generated, which can obviously increase the production cost of the paraquat.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide a production scheme of 2, 3-dimethyl-2, 3-diphenylbutane (i.e. paraquat) which can realize the recycling of the free radical initiator. And the scheme can be combined with the process for producing the propylene oxide by the hydrogen peroxide cumene method (namely CHP-PO process) which is industrially practiced at present, and the equipment investment and the operation cost are reduced to the maximum extent by sharing certain reaction units.
In one aspect, the present invention provides a method for preparing 2, 3-dimethyl-2, 3-diphenylbutane, comprising:
cumene is subjected to a free radical coupling reaction under the action of dicumyl peroxide to give a product stream containing 2, 3-dimethyl-2, 3-diphenylbutane.
The inventor of the present application finds that dicumyl peroxide (DCP) is used as a radical initiator, so that cumene can be effectively promoted to generate paraquat, new impurities are prevented from being introduced into a system, and the combination with a CHP-PO process is facilitated. The principle of the method is probably that DCP can induce cumene to generate an isopropylbenzene free radical, the isopropylbenzene free radical is coupled to generate the paraquat, and the DCP is sloughed into alpha, alpha-dimethylbenzyl alcohol.
In addition, in the invention, the isopropyl benzene can also play a role of a solvent, and raw materials and products of DCP, paraquat, alpha-dimethyl benzyl alcohol and the like can be ensured to be dissolved in a liquid phase.
In some preferred embodiments of the invention, the cumene contains less than 1000ppm, preferably less than 200ppm, phenolic compounds based on phenol.
In some preferred embodiments of the present invention, the dicumyl peroxide has a phenolic compound content of less than 1000ppm, preferably less than 200ppm, based on phenol.
According to the invention, certain impurities which may be entrained in cumene or DCP have an inhibitory effect on the formation of dicumyl, phenols being explicitly mentioned here. Such as phenol, resorcinol, hydroquinone, etc., and therefore the phenolic content of the feed should be as low as possible. The inventors of the present application have found through a great deal of experiments and studies that the content of phenolic compounds is less than 1000ppm, preferably less than 200ppm, based on phenol, which can ensure the smooth progress of the reaction.
In some preferred embodiments of the present invention, the dicumyl peroxide is used in an amount of 5wt% to 50wt%, preferably 10wt% to 25wt%, based on the total mass of the cumene and the dicumyl peroxide.
In some preferred embodiments of the present invention, the conditions of the radical coupling reaction include: the reaction temperature is 50-200 ℃, preferably 100-150 ℃; the reaction time is 1-72 h, preferably 6-12 h.
According to the present invention, the high temperature is advantageous for increasing the reaction rate, but decreases the selectivity of the objective product, such as the formation of acetophenone, which may be a by-product, and thus, in order to simultaneously achieve a high reaction rate and a high selectivity, the present invention limits the reaction temperature of the radical coupling reaction to 50 ℃ to 200 ℃, preferably 100 ℃ to 150 ℃.
According to the invention, when the reaction temperature is lower, the reaction time can be properly prolonged to improve the yield of the paraquat. In the above temperature range, the reaction time of the radical coupling reaction is 1 to 72 hours, preferably 6 to 12 hours.
According to the invention, the reaction pressure for the free-radical coupling reaction is atmospheric or slightly positive. Cumene has a boiling point of 152 ℃ at atmospheric pressure and is capable of performing a liquid phase reaction at atmospheric pressure within the temperature range of the present invention.
According to the invention, a slight positive pressure means a pressure of not more than 50 kPa.
According to the present invention, the reaction atmosphere for the radical coupling reaction may be air or an inert atmosphere. In fact, the presence of air does not affect the effect of the reaction itself, on the premise of ensuring safety.
According to the invention, the free radical coupling reaction may be carried out with or without a catalyst. If a catalyst is used, the catalyst is usually selected from organic acid salts of metal ions such as Fe (II), co (II) and the like, such as ferrous acetate and cobalt acetate. The dosage of the catalyst is not more than 5 percent of the total mass of the reaction raw materials. However, these salts may precipitate and be carried into the product of the paraquat, and the use of the above-mentioned catalyst should be avoided when the requirement for the use of paraquat is limited. In fact, by adjusting the conditions of temperature and reaction time, etc., the desired technical effect can be achieved without using a catalyst.
In some preferred embodiments of the present invention, the above preparation method further comprises: the product stream containing 2, 3-dimethyl-2, 3-diphenylbutane is subjected to a distillation under reduced pressure to obtain a first desired product stream enriched in 2, 3-dimethyl-2, 3-diphenylbutane and a first by-product stream enriched in α, α -dimethylbenzyl alcohol.
According to the invention, after the generation of the paraquat, the main components of the system are cumene, paraquat and alpha, alpha-dimethylbenzyl alcohol, possibly with a small amount of by-products such as acetophenone, which can precipitate at higher concentrations. However, a large amount of cumene and α, α -dimethylbenzyl alcohol generally exist in the system, and therefore, it is necessary to distill off the excessive cumene, α -dimethylbenzyl alcohol and some other by-products in the liquid phase product by vacuum rectification.
In some preferred embodiments of the present invention, the conditions of the vacuum distillation process include: the vacuum degree is 10kPa-95kPa, preferably 70kPa-90kPa; the temperature of the bottom of the tower is less than 250 ℃, preferably less than 200 ℃.
According to the invention, the purpose of the vacuum distillation is to separate the components while avoiding the decomposition of the paraquat, so the principle of controlling the vacuum degree is to reduce the temperature of the bottom of the column as much as possible, preferably the temperature of the bottom of the column is not more than 250 ℃, more preferably not more than 200 ℃. Cumene and alpha, alpha-dimethyl benzyl alcohol are obtained from the top of the rectifying tower, and the tower bottom is concentrated to produce the paraquat which can be solidified or separated out after cooling.
According to the invention, the content of α, α -dimethylbenzyl alcohol in the first by-product stream is from 10wt% to 90wt%, preferably from 25wt% to 60wt%.
According to the invention, the content of α, α -dimethylbenzyl alcohol in the first by-product stream is mainly determined by the amount of dicumyl peroxide used in the production of paraquat.
According to the invention, the purity of the obtained paraquat product is more than 97%, preferably more than 98%, more preferably more than 99%.
According to the invention, the alpha, alpha-dimethylbenzyl alcohol obtained at the top of the rectification column, if not further processed, becomes a coproduct with a yield equivalent to that of paraquat. However, the present invention preferably further treats the stream enriched in α, α -dimethylbenzyl alcohol to effect recycle of the by-products.
In some preferred embodiments of the invention, a portion, preferably 25% to 75%, of the first by-product stream is subjected to a hydrogenolysis reaction with hydrogen in the presence of a hydrogenation catalyst to obtain a stream comprising cumene; and
the cumene-containing stream is subjected to an oxidation reaction with an oxygen-containing gas, preferably air, to obtain a cumene hydroperoxide-containing stream.
According to the present invention, the hydrogenolysis reaction refers to a reaction of α, α -dimethylbenzyl alcohol with hydrogen in the presence of a catalyst to produce cumene. The catalyst comprises Pd/C and Pd/SiO 2 、Pd/Al 2 O 3 And other hydrogenation catalysts commonly used in the art to meet the requirements.
According to the present invention, the molar ratio of hydrogen to α, α -dimethylbenzyl alcohol in the hydrogenolysis reaction is 1. The temperature of the hydrogenolysis reaction is 150-350 ℃. Preferably, the conditions of the hydrogenolysis reaction are determined according to the performance of the hydrogenation catalyst employed.
According to the present invention, the oxidation reaction refers to a solution in which cumene is oxidized to cumene hydroperoxide with an oxygen-containing gas, preferably air. This reaction is well known and well established in the art, particularly in the phenol acetone production process and the cumene hydroperoxide process to produce propylene oxide.
According to the invention, the temperature of the oxidation reaction is between 70 and 150 ℃ and preferably between 90 and 110 ℃.
In some preferred embodiments of the invention, the stream comprising cumene hydroperoxide is subjected to a condensation reaction with α, α -dimethylbenzyl alcohol to obtain a stream comprising dicumyl peroxide.
According to the present invention, the α, α -dimethylbenzyl alcohol may be derived from the remainder of the first by-product stream.
According to the present invention, the condensation reaction refers to a reaction of cumene hydroperoxide with α, α -dimethylbenzyl alcohol, and dehydration of the cumene hydroperoxide to produce DCP. The reaction uses perchloric acid and other acidic catalysts, the product can be separated into an organic layer and a water layer, the organic layer generally comprises cumene, DCP and unreacted dimethylbenzyl alcohol, the DCP can be directly reused in the production of the paraquat in the form of the organic solution, and the purified DCP can also be obtained through the distillation-crystallization process for reuse.
According to the invention, the conditions of the condensation reaction include: the molar ratio of the cumene hydroperoxide to the alpha, alpha-dimethyl benzyl alcohol is 0.5. The temperature of the condensation reaction is 35-45 ℃. The condensation reaction time should be such that cumene hydroperoxide is completely consumed and the excess α, α -dimethylbenzyl alcohol can remain in the system. The condensation reaction product will be recycled for re-use in initiating the formation of the paraquat wherein the residual α, α -dimethylbenzyl alcohol does not have a significant negative effect on the initiator effect.
In some preferred embodiments of the invention, the cumene hydroperoxide containing stream is used as an oxidant in olefin epoxidation reactions, preferably a feed stream comprising an olefin is contacted with the oxidant to yield a second target product stream enriched in epoxide compounds and a second by-product stream enriched in α, α -dimethylbenzyl alcohol.
In some preferred embodiments of the invention, the second byproduct stream is combined with the first byproduct stream to simultaneously carry out the hydrogenolysis reaction and the oxidation reaction.
The hydrogenolysis and oxidation reactions described above for the preparation of by-products by means of the paraquat according to the present invention are in fact also essential units in certain processes using cumene hydroperoxide for the preparation of epoxy compounds, and therefore the paraquat production process according to the present invention may be combined with the production process of these epoxy compounds, here in particular the CHP-PO process. Referring to the propylene oxide production process as described in patent CN104109140A, the CHP-PO process itself comprises three main reactions, cumene oxidation, cumene hydroperoxide epoxidation of propylene and the hydrogenolysis of dimethyl benzyl alcohol to recover cumene, wherein the specific tasks of the cumene oxidation and benzyl alcohol hydrogenolysis units are consistent with the aforementioned work-up of the co-product of the co-drying.
Moreover, if the treatment according to the invention is strictly followed, the coproduct, i.e. the aforesaid first by-product stream, whose basic composition, including some major impurities such as acetophenone and the like, is very close to the corresponding stream in the CHP-PO process, i.e. the aforesaid second by-product stream. Thus, without special treatment, the two streams can be mixed directly to a unified hydrogenolysis unit. Alternatively, the cumene oxidation stream from the CHP-PO process can be used directly to produce DCP by condensation.
Therefore, the invention claims that the combination of two processes of paraquat preparation and CHP method olefin epoxidation is realized by sharing the hydrogenolysis reaction unit and the oxidation reaction unit. It can be said that this process combination is convenient and efficient, and the equipment investment and running cost are reduced to the utmost extent.
The invention has the beneficial effects that: the method realizes the production of the paraquat under mild reaction conditions, simultaneously realizes the effective utilization of byproducts, particularly can realize the recycling of a free radical initiator, can combine the paraquat production with the CHP method olefin epoxidation process, shares part of reaction units, and reduces the investment and the cost.
Drawings
FIG. 1 is a flow chart of the production process in example 1.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
1. Preparation of paraquat
800g of cumene (the content of phenolic compounds is less than 50ppm calculated by phenol) and 200g of DCP (the content of phenolic compounds is less than 100ppm calculated by phenol) are put into a reaction kettle, and then the temperature is gradually increased to 120 ℃, and after 12 hours of reaction, the paraquat is prepared. Wherein the product composition in the reaction kettle is shown in Table 1.
TABLE 1
Components Mass fraction (%)
Isopropyl benzene 63.0
Linkuai 16.7
Alpha, alpha-dimethyl benzyl alcohol 18.8
Acetophenone 0.8
Methyl styrene 0.3
Others (C) 0.4
2. Vacuum distillation treatment
Distilling the product under the vacuum degree of 70kPa, wherein the temperature of the tower kettle is about 195 ℃, and components such as isopropyl benzene, alpha-dimethyl benzyl alcohol, acetophenone, methyl styrene and the like are collected from the top, wherein the mass fraction of the isopropyl benzene is about 77%, and the mass fraction of the alpha, alpha-dimethyl benzyl alcohol is about 20%.
The tower still is mainly made up of paraquat and small quantity of isopropyl benzene and alpha, alpha-dimethyl benzyl alcohol, after the temp. is reduced to room temp., white solid is coagulated and separated out, and then it is filtered and washed by proper quantity of isopropyl benzene, after the solvent is volatilized, the product is paraquat whose purity is greater than 97%.
3. Hydrogenolysis reaction
Reference toThe method provided in patent CN101735004A is used for hydrogenolysis, and Pd/SiO is selected as a catalyst 2 -Al 2 O 3 (catalyst reference is made to the hydrogenolysis catalyst provided in the example of CN 101733093A), in this example, some specific reaction parameters are: the reaction pressure is 1.8-2.0 MPa, the molar ratio of hydrogen to alpha, alpha-dimethyl benzyl alcohol is 10.
The results show that: the conversion of alpha, alpha-dimethylbenzyl alcohol was over 99%, and the concentration of the hydrogenolysis product, cumene, was >98%.
4. Oxidation reaction
100g of hydrogenolysis product is put into a three-neck flask, air is kept to be introduced, the temperature is heated to 97 ℃, and after reaction for 7 hours, a cumene solution of cumene hydroperoxide is obtained. The cumene hydroperoxide mass fraction was determined to be about 16.5% by iodometry.
5. Condensation reaction
In a three-necked flask, 100g of the product of the oxidation reaction (i.e., cumene solution of cumene hydroperoxide as described above) was charged and mixed with about 90g of the vacuum distillation overhead product to obtain a molar ratio of α, α -dimethylbenzyl alcohol to cumene hydroperoxide in the system of about 1.2:1, ensuring that the cumene hydroperoxide can fully react, adding 0.5g perchloric acid, fully stirring for reaction, keeping the reaction temperature of 40-45 ℃ in a water bath, separating an organic phase and a water phase after reacting for 8 hours, and respectively washing the organic phase with 4mol/L NaOH solution and water. The organic phase contains about 15% DCP, the remainder being mainly cumene and α, α -dimethylbenzyl alcohol. This phase can be directly recycled as a raw material in the first step to prepare the paraquat. Or purifying DCP by reduced pressure distillation at 95 deg.C under 15 × 133.3Pa, and reducing pressure to (1-2) × 133.3Pa to obtain crude DCP product at the same temperature. Dissolving with absolute ethyl alcohol, recrystallizing at 0 deg.C, filtering and drying to obtain DCP crystal with purity of 99%.
Example 2
Paraquat was prepared in the manner described in example 1, except that cumene was used, containing about 1500ppm phenol. The composition of the product in the autoclave after the reaction under the same conditions is shown in Table 2.
TABLE 2
Components Mass fraction (%)
Isopropyl benzene 75.0
Linkuo (Linkuai) 5.1
Alpha, alpha-dimethyl benzyl alcohol 6.1
Acetophenone 12.7
Methyl styrene 0.2
Others 0.9
Example 3
Paraquat was prepared in the manner described in example 1, except that DCP, containing about 1500ppm phenol, was used. The composition of the product in the autoclave after the same reaction conditions is shown in Table 3.
TABLE 3
Components Mass fraction (%)
Isopropyl benzene 67.1
Linkuo (Linkuai) 11.9
Alpha, alpha-dimethyl benzyl alcohol 12.5
Acetophenone 7.7
Methyl styrene 0.3
Others 0.5
From the results of example 2 and example 3, it was found that phenol in the system relatively significantly suppressed the formation of paraquat, and promoted the ineffective decomposition of a part of DCP into acetophenone.
Example 4
Paraquat was prepared as in example 1 except that DCP was used in an amount of 50g. Wherein, the composition of the product in the reaction kettle is shown in Table 4.
TABLE 4
Components Mass fraction (%)
Isopropyl benzene 87.8
Linkuo (Linkuai) 5.5
Alpha, alpha-dimethylbenzyl alcohol 5.7
Acetophenone 0.2
Methyl styrene 0.3
Others (C) 0.5
Example 5
Paraquat was prepared as in example 1 except that DCP was used in an amount of 800g. Wherein, the composition of the product in the reaction kettle is shown in Table 5.
TABLE 5
Components Mass fraction (%)
Isopropyl benzene 22.3
Linkuo (Linkuai) 26.7
Alpha, alpha-dimethylbenzyl alcohol 31.6
Acetophenone 11.5
Methyl styrene 5.2
Others 2.7
From the results of examples 4 and 5, it is understood that when the amount of DCP used in the reaction system is relatively small, the by-products such as acetophenone can be relatively reduced. The method has the disadvantages that the concentration of the paraquat in the product is low, the amount of the isopropyl benzene to be distilled in the next distillation is large, and the method is not favorable from the aspect of operation cost.
Example 6
The reaction product after the completion of the paraquat was subjected to distillation under reduced pressure in the same manner as in example 1 except that it was not conducted under vacuum conditions but conducted under normal pressure. At this time, in order to effectively separate α, α -dimethylbenzyl alcohol from the system, the temperature of the distillation column pot must be raised to 260 ℃ or more. The results show that: after benzyl alcohol is separated as much as possible, the system in the kettle becomes dark and viscous, a paraquat product separated out after cooling is in an abnormal dark brown color, and the paraquat product is re-dissolved in isopropyl benzene and analyzed through gas chromatography, so that the residual content of alpha, alpha-dimethyl benzyl alcohol is high, some unidentified impurities with high boiling points are added, and the purity of the paraquat is calculated to be about 95 percent.
Comparative example 1
Paraquat was prepared as in example 1 except that about 121 g of azobisisobutyronitrile was used in place of 200g of dcp in example 1 and finally the composition of the product in the reaction kettle is as shown in table 6.
TABLE 6
Components Mass fraction (%)
Isopropyl benzene 73.5
Linkuo (Linkuai) 15.1
Isobutyronitrile 7.1
Others (C) 4.3
From the above table, it is clear that the use of azobisisobutyronitrile as an initiator also allows to obtain a high yield of paraquat. But unlike the α, α -dimethylbenzyl alcohol produced when DCP is used, it can be reused; the byproducts of the azodiisobutyronitrile after use comprise isobutyronitrile and the like, which cannot be directly used for preparing the azodiisobutyronitrile again, and the components of the azodiisobutyronitrile have certain toxicity and higher cost of harmless treatment.
Comparative example 2
Paraquat is prepared as in example 1 except that t-butyl hydroperoxide is used in place of DCP in example 1 and, in addition, because t-butyl hydroperoxide is less stable, its amount is reduced to about 2.5wt% of cumene, i.e., 20 g, for safety, and the reaction temperature is also lowered to about 80 ℃. Finally, the composition of the product in the reactor is shown in Table 7.
TABLE 7
Components Mass fraction (%)
Isopropyl benzene 95.9
Linkuai 1.3
Tert-butyl alcohol 1.9
Others 0.9
As can be seen from the above table, the use of other organic peroxides such as t-butyl hydroperoxide as the initiator also leads to the formation of different by-products such as t-butanol after the reaction. The advantage of peroxides is the lower toxicity of the by-products compared to azo initiators. However, most of the peroxide by-products are not like DCP and alpha, alpha-dimethyl benzyl alcohol systems, which have a mature and reliable recycling method, and can depend on CHP-PO process equipment with larger scale. Meanwhile, the application of the peroxide needs to consider the stability, and the peroxide with better stability like DCP is obviously more convenient to use.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (7)

1. A method for preparing 2, 3-dimethyl-2, 3-diphenylbutane, which comprises the following steps:
(1) Subjecting cumene to a free radical coupling reaction under the action of dicumyl peroxide to obtain a product stream containing 2, 3-dimethyl-2, 3-diphenylbutane;
(2) Subjecting the product stream containing 2, 3-dimethyl-2, 3-diphenylbutane to a distillation under reduced pressure to obtain a first desired product stream enriched in 2, 3-dimethyl-2, 3-diphenylbutane and a first by-product stream enriched in α, α -dimethylbenzyl alcohol;
(3) Subjecting a portion of the first by-product stream to a hydrogenolysis reaction with hydrogen in the presence of a hydrogenation catalyst to obtain a stream comprising cumene; and subjecting the stream comprising cumene to an oxidation reaction with an oxygen-containing gas to obtain a stream comprising cumene hydroperoxide;
(4) Condensing the cumene hydroperoxide containing stream with the remainder of the first byproduct stream to produce a dicumyl peroxide containing stream; or contacting a feed stream comprising olefins with the cumene hydroperoxide containing stream to yield a second target product stream enriched in epoxy compounds and a second byproduct stream enriched in α, α -dimethylbenzyl alcohol, the second byproduct stream being combined with the first byproduct stream to simultaneously perform the hydrogenolysis reaction and the oxidation reaction;
wherein, the total mass of the cumin and the dicumyl peroxide is taken as a calculation reference, and the dosage of the dicumyl peroxide is 10-25 wt%;
wherein the cumene and the dicumyl peroxide have a phenolic compound content of less than 1000ppm based on phenol.
2. The method according to claim 1, wherein the cumene and the dicumyl peroxide have a content of phenolic compounds of less than 200ppm in terms of phenol.
3. The production method according to claim 1 or 2, wherein the conditions of the radical coupling reaction include: the reaction temperature is 50-200 ℃; the reaction time is 1-72 h.
4. The production method according to claim 3, wherein the conditions of the radical coupling reaction include: the reaction temperature is 100-150 ℃; the reaction time is 6-12 h.
5. The production method according to claim 1, wherein the conditions of the reduced pressure distillation treatment include: the vacuum degree is 10kPa-95kPa; the temperature of the tower kettle is less than 250 ℃.
6. The production method according to claim 5, wherein the conditions of the reduced pressure distillation treatment include: the vacuum degree is 70kPa-90kPa; the temperature of the tower kettle is less than 200 ℃.
7. The method of claim 1, wherein the portion of the first byproduct stream is 25% to 75% of the first byproduct stream.
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