JP5858830B2 - Process for producing polychloropropane - Google Patents

Description

  The present invention relates to a process for producing polychloropropane. More specifically, 1,1,1,3-tetrachloropropane is produced from carbon tetrachloride and ethylene as raw materials, using an iron-phosphate ester catalyst, and reacted with chlorine to produce 1,1,1, The present invention relates to a production method for conversion to 1,2,3-pentachloropropane.

  Polychloropropane is important as a raw material or intermediate for producing various products such as agricultural chemicals, pharmaceuticals, and CFC substitute materials. The target compound 1,1,1,2,3-pentachloropropane starts from 1,1,2,3-tetrachloropropene to produce trichloroallyldiisopropylthiocarbamate useful as a herbicide. Can do.

  As a method for producing such a chlorinated hydrocarbon, for example, a first reaction for obtaining chloropropane by adding carbon tetrachloride to an unsaturated compound having 2 carbon atoms (unsubstituted or chlorine-substituted ethylene), and the chloropropane A two-stage reaction is known which comprises a second reaction in which dehydrochlorination and chlorination are simultaneously carried out to obtain the desired chloropropane.

  Of these, the first reaction is, for example, in Patent Document 1, in which an addition reaction between ethylene and carbon tetrachloride is performed in the presence of an iron-phosphoryl compound catalyst to obtain 1,1,1,3-tetrachloropropane. Have been described.

  In addition, the subsequent second reaction is a method in which 1,1,1,3-tetrachloropropane is dehydrochlorinated and chlorinated simultaneously to obtain 1,1,1,2,3-pentachloropropane as a catalyst. There has been proposed a method for obtaining 1,1,1,2,3-pentachloropropane at once by using iron chloride and blowing chlorine gas into 1,1,1,3-tetrachloropropane under heating (Patent Document). 2).

  For the second step, the present inventors have already proposed a method in which aluminum chloride is used as a catalyst and the reaction proceeds under cooling.

Japanese Examined Patent Publication No. 2-47969 US Patent Publication No. 2009/216055

  However, according to the study by the present inventors, the progress of the reaction was often inhibited in the second step.

  As a result of intensive studies in view of the above problems, the present inventors have found that specific impurities in 1,1,1,3-tetrachloropropane in the second step hinder the progress of the reaction, and the impurities It was found that the reaction to 1,1,1,2,3-pentachloropropane proceeded rapidly by setting the concentration below the specified value, and the present invention was completed.

That is, the present invention is a process for obtaining 1,1,1,3-tetrachloropropane by reacting carbon tetrachloride produced by reaction of chlorine and methyl chloride and / or by reaction of methanol and hydrogen chloride with ethylene. 1,1,1,3-Tetrachloropropane obtained in the first step and the first step is dehydrochlorinated and chlorinated using a Lewis acid catalyst to obtain 1,1,1,2,3-pentachloropropane. In the process for producing 1,1,1,2,3-pentachloropropane comprising the second step,
1,1,1,2,3 including a step of adjusting the total bromine content in 1,1,1,3-tetrachloropropane to 30 ppmw or less at least before the start of the second step -A process for producing pentachloropropane.

  According to the present invention, 1,1,1,3-tetrachloropropane is produced using carbon tetrachloride and ethylene, and then converted to 1,1,1,2,3-pentachloropropane in the presence of a Lewis acid catalyst. In the production method having a conversion reaction step, the reaction can proceed stably. Therefore, it is extremely useful industrially.

  Hereinafter, the present invention will be described in detail. In the present invention, carbon tetrachloride produced by the reaction of chlorine and methyl chloride and / or by the reaction of methanol and hydrogen chloride is reacted with ethylene to obtain 1,1,1,3-tetrachloropropane. And 1,1,1,3-tetrachloropropane obtained in the first step are dehydrochlorinated and chlorinated using aluminum chloride to obtain 1,1,1,2,3-pentachloropropane. Including at least two steps of the second step, and further including a step of adjusting the total bromine content in 1,1,1,3-tetrachloropropane to 30 ppmw or less before the start of the second step. .

  First, the second step will be briefly described. In this step, dehydrochlorination occurs from 1,1,1,3-tetrachloropropane using Lewis acid as a catalyst, and trichloropropene is generated. Here, if chlorine is present in the reaction system, chlorine addition to the double bond of the trichloropropene occurs rapidly using the same Lewis acid as a catalyst, and apparently 1,1,1,3 in one reaction. -1,1,1,2,3-pentachloropropane is produced from tetrachloropropane.

  According to the study by the present inventors, if a bromine compound is present in the reaction system in this step, the mechanism is unclear but the reaction is hindered, and 1,1,1,2,3-pentachloropropane is stably obtained. Is difficult. Since the bromine compound can exist in a plurality of states having different chemical structures, in the present invention, the abundance is defined not by the bromine compound concentration but by the total bromine (Br) concentration.

  The reason why the bromine compound is mixed into the reaction system is that carbon tetrachloride used in the first step is tetrachloride produced by reaction of chlorine and methyl chloride and / or by reaction of methanol and hydrogen chloride. The use of carbon.

  In general, bromine derived from a raw material salt exists in chlorine, and therefore bromine compounds are contained as impurities of carbon tetrachloride when chlorinating methyl chloride to produce carbon tetrachloride. Further, since hydrogen chloride is also synthesized by combustion of chlorine and hydrogen or by-product hydrochloric acid for chlorination reaction, bromine compounds derived from the raw material salt for chlorine production are also included.

  The bromine compound does not affect the reaction between carbon tetrachloride and ethylene in the first step, but as mentioned above, it becomes an interfering substance in the second step, so it must be removed before starting the second step. It is. In addition, as a bromine compound contained in carbon tetrachloride, the compound by which 1 to 4 of the chlorine of carbon tetrachloride was substituted with bromine, specifically, bromodichloromethane, bromotrichloromethane, etc. are mentioned. Since these bromine compounds are converted to brominated chloropropane through the first step, the amount of bromine compounds tends to be greater after completion of the first step than before the start of the first step. .

  As long as the removal of the bromine compound is before the start of the second step, it may be before the first step, or after the completion of the first step and before the start of the second step. Column separation, distillation purification and the like. The first process is completed in that the process can be simplified by removing other impurities (for example, isomers with different chlorinated positions or different number of chlorinated compounds) generated in the first process. Then, it is preferable to purify by distillation before the start of the second step.

  In the production of the carbon tetrachloride, a radical initiator composed of an azo compound may be used. According to the study by the present inventors, a compound having a cyano group produced by decomposition of the azo compound is also described. Interfere with the two-step reaction.

  Therefore, when carbon tetrachloride having such a compound having a cyano group as an impurity is used as a raw material, it is effective to remove the compound having the cyano group before the start of the second step. Desirable to obtain. If the removal is also before the start of the second step, it may be before the first step, or after the completion of the first step and before the start of the second step. The removal method is not particularly limited, and examples include adsorption removal, column separation, and distillation purification. Removal by distillation is preferable because it can be removed simultaneously with the bromine compound. The concentration at the time of removal is preferably 30 ppmw or less, more preferably 10 ppmw or less.

  More specifically, the purification by distillation is as follows when performed before the first step.

  As the distillation column used for the distillation, those known in the art can be used without limitation, and a plate column or a packed column can be mentioned as a preferable one. There is no limit to the number of stages of the column tower or the equivalent number of stages of the distillation column converted into a column tower, but if it is too much, the cost of the distillation equipment increases, so it is preferably 1 to 50 stages, and 10 to 30 stages. Is more preferable. The distillation tower may be performed in one tower or several towers. As the above-mentioned column tower, a cross flow tray, a shower tray, or the like can be used.

  As a packing in the case of using a packed distillation apparatus, a known packing such as a Raschig ring or a Lessing ring may be used, and the material is not limited, and various metals can be used.

  There are no particular restrictions on the conditions for carrying out the distillation, and it can be carried out at normal pressure (101 kPa), and the temperature at the top of the distillation column can be performed even near the boiling point of carbon tetrachloride, but if the temperature at the top of the distillation column is too high ( (The temperature at the bottom of the column also rises) Carbon tetrachloride tends to decompose, and if the temperature at the top of the distillation column is too low, the energy for cooling the top of the distillation column will increase during distillation, and the pressure must be very low. Therefore, the cost of the equipment and the operating cost become high. Therefore, the temperature range at the bottom of the column during distillation is preferably 20 ° C to 130 ° C, more preferably 40 ° C to 120 ° C, and more preferably 50 ° C to 100 ° C. Regarding the pressure at the time of distillation, carbon tetrachloride is vaporized at the above-mentioned temperature, and can be performed at a pressure that reaches the upper part of the distillation column. The pressure is preferably 1 kPa to 110 kPa. The pressure here is an absolute pressure.

  By performing distillation purification while confirming the distillate component by this distillation operation, it is possible to purify carbon tetrachloride before the first step and to reduce the total bromine (impurity) amount to 30 ppmw or less.

  Further, the purification of 1,1,1,3-tetrachloropropane after the first step and before the second step is not particularly limited in conditions for distillation, and is performed at normal pressure (101 kPa). Can be carried out even near the boiling point of 1,1,1,3-tetrachloropropane, but if the temperature at the top of the distillation column is too high (the temperature at the bottom of the column also increases), 1,1,1,3- Tetrachloropropane is easily decomposed, and if the temperature at the top of the distillation column is too low, the energy for cooling the top of the distillation column is increased during distillation, and the pressure must be kept very low. It will be expensive. Therefore, the temperature range at the bottom of the column during distillation is preferably 20 ° C to 200 ° C, more preferably 50 ° C to 150 ° C, and more preferably 70 ° C to 120 ° C. Regarding the pressure at the time of distillation, 1,1,1,3-tetrachloropropane is vaporized at the above temperature and the pressure reaching the upper part of the distillation tower can be used, but the pressure is preferably 1 kPa to 110 kPa. The pressure here is an absolute pressure.

  By performing distillation purification while confirming the distillate component by this distillation operation, the total bromine (impurity) amount in 1,1,1,3-tetrachloropropane is 30 ppmw or less after the first step and before the second step. Is possible.

  In the case of distillation, it is not particularly necessary to add an additive, but a stabilizer may be added to suppress decomposition. Examples of the stabilizer include various phenols, for example, phenols substituted with an alkoxy group and phenols substituted with an allyl group. Specific examples of phenols substituted with an allyl group include o-allylphenol, m-allylphenol, p-allylphenol, 4-allyl-2-methoxyphenol (eugenol), 2-methoxy-4- (1 -Propenyl) phenol (isoeugenol) and the like. These allyl-substituted phenols may be used alone or in combination.

  There is no particular limitation on the method for measuring the amount of chloropropane, bromine compounds, and other impurities represented by 1,1,1,3-tetrachloropropane. For example, gas chromatography is used for separation, and flame ionization is used for the detector. Each can be quantified using a mold detector (FID). In addition to FID, a thermal conductivity detector, a mass analyzer, or the like can be used, and there is no particular limitation. The total amount of bromine can be easily determined from the amount of bromine compound detected by a conventional method.

  In the present invention, the first step of obtaining 1,1,1,3-tetrachloropropane by reacting carbon tetrachloride with ethylene is a known method, for example, JP 2012-36190 A, JP 2011-57650 A. What is necessary is just to implement by the method as described in the gazette.

  Briefly describing the method, carbon tetrachloride is filled in a reaction vessel, and ethylene gas is introduced into the vessel at a predetermined rate. At this time, by adding an iron-phosphate ester catalyst in the reaction system, the addition of carbon tetrachloride to ethylene proceeds smoothly, and the target 1,1,1,3-tetrachloropropane is reduced. Obtained with high efficiency.

  In the second step of the present invention, the 1,1,1,3-tetrachloropropane obtained as described above was subjected to dehydrochlorination / chlorination using a Lewis acid catalyst to produce 1,1,1,1. It is a step for obtaining 2,3-pentachloropropane, and it is necessary to keep the total bromine amount to 30 ppmw or less before starting this step as described above. -The second step from tetrachloropropane to 1,1,1,2,3-pentachloropropane will be described. First, 1,1,1,3-tetrachloropropane placed in a reaction vessel is converted to iron chloride, aluminum chloride. 1,1,3-trichloropropene is produced as a reaction intermediate resulting from the dehydrochlorination reaction using a Lewis acid as a catalyst, followed by the addition of a salt to the double bond of the 1,1,3-trichloropropene. It is estimated that 1,1,1,2,3-pentachloropropane is added to form a Lewis acid, and the reaction proceeds at a relatively low temperature, the conversion rate and the like are good, and bromine Aluminum chloride is particularly preferred from the standpoint of significant interference by minutes.

  The case where aluminum chloride is used as a catalyst with Lewis acid as an example will be described in more detail as follows. In the first embodiment, chloropropane and anhydrous aluminum chloride as described above are placed in a reaction vessel, and then chlorine is introduced into the reactor. When anhydrous aluminum chloride is not used, the target reaction does not proceed selectively. Further, by using aluminum chloride, the desired reactant can be obtained at a much lower temperature and with a higher selectivity than when other metal chlorides such as iron chloride are used.

  In addition, when there is no dissolved aluminum chloride in the reaction system, the dehydrochlorination reaction to 1,1,3-trichloropropene by dehydrochlorination of 1,1,1,3-tetrachloropropane is 1 , 1,1,3-Tetrachloropropane undergoes a substitution reaction of chlorine, and by-products such as 1,1,1,3,3-pentachloropropane are produced, and the desired 1,1,1,1, The selectivity for 2,3-pentachloropropane tends to decrease.

  Therefore, it is desirable to supply chlorine after at least a part of anhydrous aluminum chloride is dissolved and the dehydrochlorination reaction is started, and it is important to appropriately adjust the amount of dissolution of anhydrous aluminum chloride. Whether or not anhydrous aluminum chloride is dissolved can be confirmed by a change in the color tone of the reaction solution. Specifically, the liquid that is almost colorless is colored blue.

  As aluminum chloride to be used, anhydrous aluminum chloride is used. Aluminum chloride hexahydrate is substantially insoluble in 1,1,1,3-tetrachloropropane. In addition, aluminum hydroxide produced by the reaction of aluminum chloride with water does not serve as a catalyst for the dehydrochlorination reaction. However, even if aluminum hydroxide or aluminum chloride hexahydrate is contained in the system, the reaction is not particularly adversely affected.

  Further, when the amount of anhydrous aluminum chloride dissolved in the reaction system is too large, 1,1,3-trichloropropenes produced by dehydrochlorination reaction of 1,1,1,3-tetrachloropropane, or chloropropenes Since dimerization by the reaction between chloropropane and chloropropane proceeds, the selectivity of the desired 1,1,1,2,3-pentachloropropane tends to decrease.

Therefore, the amount of anhydrous aluminum chloride used is preferably 2.0 × 10 ^{−5 to} 2.0 × 10 ⁻² mol, more preferably ⁵ mol per mol of 1,1,1,3-tetrachloropropane. It is 0.0 * 10 < ^-5 > -1.0 * 10 < ^-3 > mol. In other words, when the total amount of anhydrous aluminum chloride is dissolved, it is preferably used so that the concentration is in the above range.

As described above, anhydrous aluminum chloride reacts (hydrolyzes) with water to become aluminum hydroxide. Accordingly, the amount of the anhydrous aluminum chloride is an amount substantially present in the reaction system. In other words, when water is contained in chloropropane as a raw material, the water and anhydrous aluminum chloride react to produce aluminum hydroxide, and the equivalent amount of water (water 3 per 1 mole of anhydrous aluminum chloride). It is sufficient to add a large amount of anhydrous aluminum chloride by the amount of (mol), so that the above amount is obtained. More specifically, the amount of anhydrous aluminum chloride actually used is 2.0 × 10 ^{−5 to} 2.0 × 10 ⁻² mol per 1 mol of chloropropane in addition to the equivalent amount of water contained in chloropropane. Is more preferable, and it is 5.0 * 10 < ^-5 > -1.0 * 10 < ^-3 > mol.

  Either chloropropane or anhydrous aluminum chloride may be fed into the reactor first. In addition to the batch reaction and the continuous reaction, a predetermined amount may be supplied at a time at first, or may be arbitrarily divided or continuously supplied during the reaction. Furthermore, anhydrous aluminum chloride may be dissolved in chloropropane outside the reactor, and this solution may be introduced into the reactor.

  A second embodiment is a method of preparing a solution of aluminum chloride outside the reactor and placing it in the reactor to prepare a solution in which aluminum chloride is dissolved in 1,1,1,3-tetrachloropropane. is there. As the aluminum chloride source to be used, anhydrous aluminum chloride can be used as in the case of preparing in the reactor described above. Further, the solvent in this case is not particularly limited as long as it does not inhibit the reaction of the present invention and can dissolve aluminum chloride, but it is a reaction substrate in consideration of purification operations such as impurity removal after the completion of the reaction. 1,1,1,3-tetrachloropropane is preferred.

  Other usable solvents include aluminum chloride, chlorine, carbon-carbon double bonds, etc., considering the yield and recovery of the desired product 1,1,1,2,3-pentachloropropane after completion of the reaction. A solvent having a boiling point different from that of the target product is preferable. Specific examples include various solvents such as chloromethane such as carbon tetrachloride and chloroform, and ethers such as tetrahydrofuran, dioxane and diethyl ether.

  As another method for preparing the aluminum chloride solution outside the reactor, metallic aluminum is added to the solvent, and chlorine and / or hydrogen chloride is introduced into the solvent to convert the metallic aluminum into aluminum chloride. It is a method to prepare. The solvent to be used is the same as the method using anhydrous aluminum chloride. In this method, insoluble impurities may be generated depending on the purity of the metal aluminum. It is preferable to introduce such an insoluble substance into the reactor after removing the prepared aluminum chloride solution by filtration or the like.

  In the above-described method for preparing an aluminum chloride solution outside the reactor, the concentration of aluminum chloride is adjusted to a high concentration and mixed with 1,1,1,3-tetrachloropropane in the reactor. In general, the concentration of the aluminum chloride falls within the above range.

  A third embodiment is a method for preparing a chloropropane solution of aluminum chloride from metal aluminum in a reactor. In the chlorination in this case, it is preferable to use hydrogen chloride because chlorine tends to cause a side reaction. Specifically, 1,1,1,3-tetrachloropropane and metal aluminum are placed in the reactor, and hydrogen chloride is introduced therein. In this case, it is preferable to use a dried hydrogen chloride. The amount of metal aluminum used may be an amount in which the aluminum chloride concentration falls within the above range when the total amount of the metal aluminum is converted into aluminum chloride.

  Moreover, you may implement combining said 1st thru | or 3rd method suitably. The first aspect is most preferable from the viewpoints of apparatus cost, operation time, purity of the obtained aluminum chloride solution, and ease of concentration control.

  In the presence of aluminum chloride, 1,1,1,3-tetrachloropropane dehydrochlorination occurs. This reaction is promoted at higher temperatures. Here, when chlorine is not supplied into the reaction system, there is a tendency to dimerize the dehydrochlorinated compounds with each other, or to proceed to a by-product by further reaction. Therefore, after mixing 1,1,1,3-tetrachloropropane and anhydrous aluminum chloride, the temperature of the reaction solution is preferably maintained within a range of 50 ° C. or less until the supply of chlorine is started. More preferably, it is 40 degrees C or less. On the other hand, if the temperature is too low, dissolution of anhydrous aluminum chloride or metal aluminum is slow, and the concentration of aluminum chloride in the reaction system tends to be difficult to enter the above-mentioned range, so 0 ° C or higher is preferable, and more preferably 10 ° C or higher. is there.

  In the first aspect, the total amount of 1,1,1,3-tetrachloropropane and anhydrous aluminum chloride used in the reactor is introduced, and preferably after the dissolution of the aluminum chloride is confirmed, the reactor is introduced into the reactor. Supply chlorine. In the second embodiment, if the insoluble matter is removed by filtration or the like, it is not necessary to confirm dissolution in the reactor. In the third aspect, it is preferable to introduce chlorine after introducing hydrogen chloride until the total amount of metallic aluminum is dissolved. As the chlorine, general industrial chlorine can be used.

  When chlorine is introduced in a state where the concentration of 1,1,1,3-tetrachloropropane is high and the concentration of 1,1,3-trichloropropene is low, in addition to the dehydrochlorination reaction of the chloropropane A chlorine substitution reaction occurs in a competitive reaction. As a result, 1,1,1,3,3-pentachloropropane is likely to be generated by the chlorine substitution reaction.

  On the other hand, if the concentration of 1,1,3-trichloropropene in the reaction system becomes too high, side reactions such as reaction between the chloropropenes and reaction between the chloropropene and chloropropane are likely to occur as described above. Become.

  Therefore, the production method of the present invention can be carried out at a higher selectivity by setting the concentration of aluminum chloride in the reaction system within the above range, and setting the timing and supply rate of chlorine supply to an appropriate range. it can. Specifically, at the start of supply of chlorine, the concentration of 1,1,3-trichloropropene by dehydrochlorination reaction is preferably 0.1 wt% to 30 wt%, more preferably 0.5 wt% to 20 wt%. It's a good idea to start at that point. The conversion rate of chloropropane can be easily determined from gas chromatographic analysis, the total amount of hydrogen chloride discharged to the gas phase, or the temperature change of the reaction solution when the heat removal amount is constant. The concentration in the reaction system can be easily grasped from the amount of chlorine.

  In consideration of the reaction efficiency, the final supply amount of chlorine is preferably 0.9 mol or more, more preferably 1 mol or more per 1 mol of 1,1,1,3-tetrachloropropane. Preferably, 1.1 mol or more is supplied. On the other hand, even if too much, useless chlorine which does not contribute to the reaction increases, so that it is preferably 2.5 mol or less, more preferably 2. mol per mol of 1,1,1,3-tetrachloropropane. 0 mol or less.

  The chlorine supply method may be initially supplied at a time (introduced into the reactor), but in this case, since side reactions are likely to occur as described above, it is preferable to supply gradually over a certain period of time. Although this supply time depends on the reaction temperature, the size of the reactor, etc., it is generally 0.5 to 20 hours, preferably about 1 to 10 hours. Moreover, when supplying over time, you may supply continuously and may supply intermittently.

  More preferably, the chlorine supply rate is adjusted so that the proportion of 1,1,3-trichloropropene in the reaction system is preferably 30 wt% or less, more preferably 20 wt% or less, and even more preferably 10 wt% or less. . Further, it is preferable to adjust the chlorine supply rate so that the chlorine concentration in the reaction system is preferably 10 wt% or less, more preferably 5 wt% or less, further preferably 3 wt% or less, and particularly preferably 1 wt% or less.

  The optimum chlorine supply amount for maintaining the above 1,1,3-trichloropropene and chlorine concentration in the reaction system varies depending on the temperature, but when the reaction temperature is 0 to 50 ° C., the raw material is initially charged. Preferably it is 1-2000 ml / min, More preferably, it is 5-1000 ml / min, More preferably, it is 10-500 ml / min with respect to 1 mol of chloropropane. Furthermore, in order to set the chlorine concentration in the reaction system within the above range, it is also preferable to change the flow rate in the above range during the reaction.

  For example, anhydrous aluminum chloride requires time until it is dissolved in 1,1,1,3-tetrachloropropane, so that the concentration of aluminum chloride is low at the beginning of the reaction and the dehydrochlorination reaction is delayed. Therefore, it is preferable that the chlorine supply amount is small in the initial stage and the supply amount is increased in the middle of the reaction. On the other hand, the proportion of the raw material 1,1,1,3-tetrachloropropane decreased in the late stage of the reaction, but if the chlorine concentration is high in this state, the chlorine substitution of 1,1,1,2,3-pentachloropropane is further increased. As the amount of impurities increases, it is preferable to reduce the supply amount of chlorine. From these things, after starting the chlorine supply, when the raw material 1,1,1,3-tetrachloropropane is preferably 95 wt% or less, more preferably 90 wt% or less, the chlorine supply amount is increased, and the intended reaction When the concentration of the raw material 1,1,1,3-tetrachloropropane in the reaction system becomes 30% wt or less, more preferably 20 wt% or less, a method of reducing the supply amount of chlorine is suitable. Can be adopted.

  When introducing chlorine into the reactor, it may be introduced into the gas phase portion in the reactor, or may be carried out by inserting the introduction tube into the reaction solution and blowing it into the solution.

  The form of the present invention may be carried out by a batch reaction, and 1,1,1,3-tetrachloropropane as a raw material is continuously supplied to the reactor, and the generated 1,1,1,2,3 is produced. It is also possible to carry out a continuous reaction with continuous extraction of pentachloropropane. In this case, since anhydrous aluminum chloride is also taken out, it is preferable to additionally supply so that the amount of anhydrous aluminum chloride in the reaction system falls within the above range. For additional supply, chloropropanes such as concentrated anhydrous aluminum chloride 1,1,1,2,3-pentachloropropane are separately prepared, and 1,1,1,3-3- There is a method of separately supplying tetrachloropropane and solid anhydrous aluminum chloride, but the latter method of supplying separately is preferable because it does not cause unnecessary impurities.

  For the same reason as described above, the temperature during supply of chlorine is also preferably maintained within a range of 0 to 50 ° C, more preferably 0 to 40 ° C, and further preferably 10 to 40 ° C. . Of the reactions that occur in the production method of the present invention, the chlorine addition reaction is an exothermic reaction, and the reaction as a whole is an exothermic reaction. System cooling is required. As the cooling (temperature adjustment of the reaction system), a method known in chemical engineering can be employed without any particular limitation.

  When the reaction is carried out batchwise, it is preferable to hold at the above temperature for about 0.1 to 2 hours after the introduction of the entire amount of chlorine into the reactor.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further more concretely, this invention is not limited to these experiment examples.

Example 1
Carbon tetrachloride produced by reaction of chlorine and methyl chloride was prepared as a raw material. The purity of this carbon tetrachloride is 92 wt%, chloroform is 6 wt%, the total bromine content in carbon tetrachloride (total amount of bromine contained alone and as a compound) is 1500 ppmw, the total cyano group content in carbon tetrachloride ( 1000 ppmw of cyano groups contained alone and as a compound). This was used as a filler in a tube having an inner diameter of 30 mm and HELI PAC NO. Using a distillation column packed with a height of 2 to 150 cm, the liquid temperature was set to 85 ° C., and batch distillation was performed at normal pressure.

The total bromine content (total amount of bromine contained alone and as a compound) contained in the obtained purified carbon tetrachloride was 10 ppmw, and the cyano compound was 5 ppmw or less.
A SUS autoclave (with an internal volume of 1500 mL) having a stirrer, an ethylene gas introduction port and a gas discharge port, a carbon tetrachloride and iron addition port, a phosphate ester addition port, and a liquid discharge port was filled with ethylene. An autoclave was charged with 1560 g of carbon tetrachloride purified by the above method, 2.0 g of triethyl phosphate and 4.0 g of K100 (Joke Steel Co., Ltd. coke reduced iron powder), and the temperature was set to 110 ° C. The addition reaction was performed by supplying ethylene so that the total pressure of the phase was 0.5 MPaG.

  The ethylene partial pressure in the gas phase immediately after the total pressure in the gas phase reached 0.5 MPaG was 0.25 MPaG.

  From the time when the temperature reached 110 ° C. and the total pressure in the gas phase reached 0.5 MPaG, triethyl phosphate was continuously added at 0.02 ml / min until the reaction was completed.

  During the reaction, ethylene is supplied so that the total pressure in the gas phase is maintained at 0.5 MPaG, and the ethylene consumption rate (additional supply rate) is 0.1 mol% /% of the initial amount of carbon tetrachloride. The reaction was judged to be complete when the minute (200 ml / min) was reached, and the addition reaction was completed.

  The liquid after the reaction was extracted and analyzed by gas chromatography (hereinafter abbreviated as GC). The conversion of carbon tetrachloride was 97% and the selectivity to 1,1,1,3-tetrachloropropane was 96%.

  1500 g of the extracted reaction liquid was put into a 1 L flask, the liquid temperature was set to 90 ° C., the pressure was set to 10 kPa (abs), and batch distillation was performed. The distillation tower is a HELI PAC NO. What filled 2 to 90 cm in height was used. The total amount of the liquid condensed at the top of the column was recovered to obtain 1340 g of liquid. The purity of 1,1,1,3-tetrachloropropane in the recovered liquid was about 99%.

  Of the recovered liquid containing 99% of 1,1,1,3-tetrachloropropane, 182 g was put into a 200 ml four-necked eggplant flask. Thereto was further added 0.10 g of anhydrous aluminum chloride. The liquid temperature was set to 20 ° C. and stirred for 1 hour. After confirming that the liquid turned blue and the aluminum chloride was dissolved, chlorine was allowed to flow in at 120 ml / min while maintaining the liquid temperature at 20 ° C. After 4 hours, the inflow of chlorine was stopped and nitrogen was circulated to expel chlorine. The reaction solution was analyzed by GC. The conversion of 1,1,1,3-tetrachloropropane was 100%, and the selectivity of 1,1,1,3-tetrachloropropane to 1,1,1,2,3-pentachloropropane was 94%.

Comparative Example 1
The first step was performed in the same manner as in Example 1 using carbon tetrachloride that had not been purified. The liquid after the reaction was extracted and analyzed by GC. The conversion of carbon tetrachloride was 97% and the selectivity to 1,1,1,3-tetrachloropropane was 96%.

  Batch distillation was performed in the same manner as in Example 1 using the obtained 1,1,1,3-tetrachloropropane crude product. The purity of the obtained 1,1,1,3-tetrachloropropane is about 99%, the total bromine content (alone and the total bromine content contained as a compound) is 500 ppmw, the total cyano group content (included alone and as a compound) The total amount of cyano groups) was 100 ppmw.

  Using this 1,1,1,3-tetrachloropropane, the second step was carried out in the same manner as in Example 1. Although aluminum chloride dissolved and the liquid turned blue, the reaction did not proceed and the liquid composition did not change.

Example 2
Batch distillation was performed using the 1,1,1,3-tetrachloropropane crude product obtained by performing the first step in the same manner as in Comparative Example 1. At this time, 75% of the liquid condensed at the top of the column was returned to the distillation column using a reflux machine, and 25% was recovered. The purity of the obtained 1,1,1,3-tetrachloropropane was about 99%, and contained 30 ppmw of the total bromine content (alone and the total bromine content contained as a compound). A compound having a cyano group was not detected.

  Using this 1,1,1,3-tetrachloropropane, the second step was performed in the same manner as in Example 1. As a result, the reaction proceeded in the same manner as in Example 1, and 1,1,1,2,3- Pentachloropropane was obtained.

Claims (3)

(1) a first step of obtaining 1,1,1,3-tetrachloropropane by reacting carbon tetrachloride produced by reaction of chlorine and methyl chloride and / or by reaction of methanol and hydrogen chloride with ethylene;
(2) 1,1,1,3-tetrachloropropane obtained in the first step is dehydrochlorinated and chlorinated using anhydrous aluminum chloride as a Lewis acid catalyst to obtain 1,1,1,2,3 A second step of obtaining pentachloropropane,
In the process for producing 1,1,1,2,3-pentachloropropane comprising
1,1,1,2,3 including a distillation step in which the total bromine content relative to 1,1,1,3-tetrachloropropane is 30 ppmw or less before at least the start of the second step -Process for producing pentachloropropane. 1,1,1,3 distillation step of the total amount of bromine is made to be less than 30ppmw for tetrachloropropane is, after completion the first step, according to claim 1, wherein performed before starting the second step 1,1,1 , 2,3-pentachloropropane production method. Four are those carbon tetrachloride were prepared in the presence of a radical initiator consisting of azo compounds, and before the start of the second step, according to claim 1 or 2, wherein comprising the step of removing impurities having a cyano group Of 1,1,1,2,3-pentachloropropane.