JPS62263134A - Manufacture of 1,1,1,3-tetrachloropropane - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improvement of the known process for producing 1,1,1,3-tetrachloropropane by reacting carbon tetrachloride with ethylene in the presence of a catalyst.

T., Asahara et al. “Industrial Chemistry Journal J (1971) 703
In two articles on pages ~705 and 2288-2290, they teach the reaction of carbon tetrachloride with ethylene in the presence of phosphites and arsenic metal salts, particularly iron chloride, to effect telomerization. There is. The reaction proceeds in various stages and produces 1,1.1.3-tetrachloroderon/4-one and relatively large amounts of high telomer. That is, (here, most of n is 1, but there are cases where n is 2 or t is 3 by a significant amount).

T, Asahara etc. are Bulletin or the
Chemical Society of Japan
A similar reaction using N-chloroalkylamines as telomerization catalysts is disclosed in a later article in J. An. Vot., 46 (1973), pages 3193-7. Small amounts of iron, copper, and their salts are added, but near the beginning of column 1 on page 3196 of the above-mentioned paper, the author states, ``The addition of iron is
- It did not affect the reactivity of chloroalkylamines."

U.S. Pat. No. 2,658,930 discloses that a mixture of ferrous metal, water and air gradually catalyzes the addition of carbon tetrachloride to 1-octene. In the only example of this reaction disclosed, carbon tetrachloride 5
The reaction for 22 days from 00.9 yielded only 10 g of addition product. For this purpose! ! 2
Although it is stated that the presence of an element is required, as will be shown later, this method has disadvantages.

Starkm is his I"F'ree
Radlcal Telomerization J A
Chapter 5 of cad@mic Press (1974) summarizes most of the vast amount of previous research on various catalysts. He describes the manner in which iron chloride works and on page 105 produces a table of initiators. Some of them are summarized above.

The object of the present invention is to provide a different catalyst system which allows the reaction to l-1-L3-tetrachlorolog-man to proceed rapidly and with high selectivity, yield and efficiency. .

According to the invention, carbon tetrachloride and ethylene are reacted in the presence of a phosphite, such as triester sulfite, and iron powder (powdered iron). Optionally, iron salts such as ferric chloride may be present. It is advantageous to exclude oxygen from the vessel in which the reaction is carried out.

The reaction can be carried out at about 70-140<0>C, with about 80-110<0>C being preferred. The vapor pressure of the liquid and the pressure due to added ethylene can range from about 25 to 500 psig, but about 70 to 150 psig.
is preferred.

The sulfites/acid esters are used in conventional amounts, for example from about 0.0005 to 0.1 mol per mol of carbon tetrachloride, preferably about 0.
．． It can be used in amounts of 0.002 to 0.02 mol. The iron powder can be of any type, but electrolytic iron and hydrogen reduced iron powders are particularly useful. The iron powder is present in an amount of at least about 0.001 mole per mole of carbon tetrachloride, preferably at least about 0.01 mole. Too much amount is not harmful and any unconsumed excess can be used in another reaction.

Smaller particle sizes (preferably less than about 50 microns) provide more surface area per unit weight and require less iron.

If desired, salts such as ferric chloride and (optionally) other initiators can be added in conventional amounts, but this is not necessary.

The reaction is advantageously carried out by adding carbon tetrachloride, phosphorous acid and iron powder as well as other initiators to the reaction vessel,
The reaction vessel is then flushed with a gas such as ethylene or brought to boiling point to remove oxygen. Seal the reactor and bring the temperature to the desired temperature for the reaction. Simultaneously, 5 reactors are pressurized to the desired level with ethylene. Ethylene is introduced periodically to maintain the pressure within the desired range. Finally, it is inevitable that the internal pressure will drop as ethylene is consumed, and that the temperature will possibly drop to about room temperature. The liquid product is removed and fractionated. Solid unreacted iron remains and is used in another cycle, optionally with some supplemental iron powder.

Between operations, the reactor can be washed with solvents such as methylene chloride, acetone and (!) water to remove inhibiting residues, but under preferred conditions without the addition of ferric chloride. In this case, this is not necessarily necessary.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Parts are by weight unless otherwise specified.

Example 1 Experiment 14: Carbon tetrachloride (CC/,
4) 947II and triethyl phosphite (σto)3p)
5.5.9 and ferric chloride (FeCts) 1.174
1 and electrolytic iron powder 7.5 I! added. Seal the container;
Alternately evacuation to 70-90 mercury and 1 with ethylene
Three pressurizations of 55 ps to 1 g were applied, which removed significant amounts of oxygen from the reactor. In this process, 46.9 carbon tetrachloride is distilled off from the reactor and 901
．． 4.9 remained. The reactor was then heated to 95°C,
The reactants were mixed by shaking the vibrating table.

When the reactor temperature approached 95°C, the reaction vessel was pressurized to 110 psig with ethylene. Ethylene was then added as needed to maintain the pressure at t-90 to 110 psig. After 11.3 hours at 95°C, the rate of ethylene uptake by the reactor decreased to a maximum of 12 hours. This indicates that the reaction was very slow. The reactor was then cooled to room temperature, and the product mixture was analyzed by chromatography (-).
, 75.9% of 1,3-tetrachloropropane, 21.21% of unreacted carbon tetrachloride, 2.4% of the second addition product, and 0.5% of other products. This is CCt4
This corresponds to a conversion of 79% and a yield of the desired product of 96.3%. When the liquid product mixture was removed from the reactor, unreacted iron powder remained in the reactor.

Experiment 15: The above reactor was heated with methylene chloride (aI2ct2
) 7% ml to dissolve the deposits attached to the wall. The methylene chloride was removed from the reactor and evaporated leaving 0.6611 ml of solid. In this state, the reactor was again ready for operation. Similar amounts of carbon tetrachloride, triethyl phosphite, and ferric chloride were newly charged, but iron powder was not added as a precaution. The reactor was operated in the same manner as above, and a carbon tetrachloride conversion of 84% and 1,
1,1,3-tetrachloroprono! A yield of 96.3 inches was obtained.

Example 2 Experiment 20: The experiment was conducted in the same reactor as in Example 1 above, except that ferric chloride was not added. 952.6 g of carbon tetrachloride, 5.4 JF of triethyl phosphite, and 7.5 g of commercial grade hydrogen-reduced iron powder were added to the reactor. Oxygen was removed in the same manner as in Example 1.
11CCC14B 56.7I in reaction 4 remained. As before, the reactor was shaken, heated to 95° C., and pressurized with ethylene to 90 to 10 ps/g. After 11.1 hours at 95°C, the reactor was cooled and the liquid product (93°C
7,51) Ik: Next to take out. A large amount of unreacted iron powder remained. The product mixture was 790.8% of 1,1,1,3-tetrachloroderon, 5.0% of unreacted carbon tetrachloride, 3.7% of the second addition product, and 0.5% of other products. Please note that this is made up of. This corresponds to a carbon tetrachloride conversion of 95% and a tetrachloride yield of 95.6%.

Experiment 21: Without cleaning the reactor, 947.2.9 of carbon tetrachloride and 5.39 of triethyl phosphite were newly charged into the reactor. However, no new iron powder was added. After desorption (902.5 J of carbon tetrachloride remaining in the reactor), the reaction was carried out at 95° C. for 11.1 hours under ethylene pressure of 90-110 pmig. Product mixture (9201
As a result of t-analysis, it was found that tetrachloroderono and 789.5
%, unreacted carbon tetrachloride 6.5%, second addition product 3.5
and 0.5 ti of other products, resulting in a carbon tetrachloride conversion of 94 ti and a tetrachloropropane yield of 95 ti.
That's equivalent to 7%.

Example 3 Experiment 32: Into a clean 9 gallon Mon*l pressure vessel, 27.200 II carbon tetrachloride was added and degassed by reflux. The vessel was then pressurized to 30 pmig with ethylene. A solution of benzoyl peroxide 495.9 in desulfurized ecz 413.6001 was added to
℃ was added slowly into the reactor. Meanwhile, the ethylene pressure was increased to 28-38 psig. According to gas chromatography, the components in the reactor were unreacted CCA462.
8 and 1.1.1.3-tetrachloropropane 31.9
1 and 3.4% of the second addition product and 1.9% of other products, corresponding to a CCt4 conversion of 37 and a desired product yield of 85.7'A. Although the conversion was low and the ethylene pressure minimized side reactions, the yield of undesirable secondary addition products was relatively high9.
Three experiments were conducted under substantially the same conditions.

The details and results are shown in the table below along with the five experiments mentioned above. Unless otherwise specified, experiments were performed in a clean reactor for 9
Performed at 0-110 psig. The mole% of catalyst used is 7+? , CCt4t- standard, and the yield is the conversion cct
4 was used as the standard.

Below margin ψ 1 Note: (1) 316 stainless steel powder 14.9JF
J-Processing.

(2) Reagent grade electrolytic iron powder was used.

(3) Iron powder remains in the reactor from the previous reaction.

(4) After 10.1 hour, the reaction was stopped using ethylene.

(5) Thoroughly clean the reactor with acetone before loading new reactants.

(6) The reactor was not washed sufficiently after the previous reaction.

(7) CH2CL before loading on new reactants.
The reactor was washed with 2.

(8) A commercially available hydrogen reduced powder was used.

(9) Commercially available iron powder (not hydrogen-reduced) was used.

It was carried out at 450 pgig.

0υ 0.57 mol of phosphite was added initially, and 0.57 mol was added 8.3 hours after the start of the reaction.

(r:to), all tributyl phosphite was used in place of p.

(To) Continuously add 0.77 mol ts of benzoyl peroxide to C
Cl2 plus nine. Reaction f, carried out at 28-3B pmig.

a→ The second addition by-product was also obtained with a yield of 9.3%.

Analyzing each of the experiments described above, the procedure according to the invention shows that when compared with the peroxide-initiated one (Experiment 32: Example 3):
It can be seen that the conversion is very high and the formation of by-products or second addition products is low.

According to experiments 1 to 4 (these are outside the scope of the present invention due to the absence of iron powder, but were otherwise conducted under similar conditions and proportions), nine large reactors were cleaned fresh with acetone and water. Among them, the highest conversion rate was found to be 43ch. Subsequent reactions leave residue on the reactor walls, which gradually reduces the efficiency of the catalyst, and in the fourth reaction the conversion drops to 24 cm.

Facts 5.6 and 7 were prepared in a clean small reactor using standard amounts of triethyl phosphite and ferric chloride.
Similarly, it is shown that the conversion rate is 43 to 48 inches. Experiment 8 shows that even with the addition of relatively large amounts of 316 stainless steel powder to the catalyst mixture, no significant effect was obtained (conversion rate 46 yen). Experiments 9 and 10 are reagent grade 1! When inert iron powder is present in the reactor along with F e C13 and (EtO)3P, the conversion rates are 83 and 87
%. At 85°C, the reaction time is twice as long as at 95°C. Similar to the description in the Japanese literature cited above, ferric chloride can be present in either the anhydrous or hexahydrate form.

Experiment 11 shows that when a small amount of iron powder is used, the conversion rate is between the conversion rate when using a large amount of iron powder (83 to 87 yen) and the conversion rate when no iron powder is used (Experiments 1.5 to 7). Conversion rate (61
%) is obtained.

Run 12 was conducted without cleaning the reactor of the residue left from Run 11. The conversion rate in Experiment 12 was low.

(45%) It is necessary to add additional iron powder just in case.
t identical to those of experiments 9 and 10, indicating that this catalyst system suffers from the same drawbacks as before (ie, the reaction is inhibited by residues from the previous reaction). However, (Eto), p is different from F@C1s, and the excess unreacted iron powder can be reused once the inhibiting residues are flushed out of the reactor.

Run 13 shows that washing the reactor with A7T after run 12 restored conversion to 84 F without adding fresh iron powder. Experiments 14 and 15 (Example 1)
shows that CH2Cl2 washes away the inhibiting deposits on the reactor walls.

Experiments 16 and 17 show that commercial grade hydrogenated iron performs similarly to the more expensive reagent grade electrolytic iron used earlier. Runs 18 and 19 showed that a cheaper, coarser grade commercially available iron powder (not hydrogen reduced) reacted even more slowly, with a conversion of only 53 g on reuse with CH2C62 cleaning of the reactor walls. It shows that there is.

Experiment 20 (Example 2) shows that when iron powder is present,
Indicates that F own CL5 is unnecessary. In fact, Fth
This iron powder-triethyl phosphite catalyst mixture, which in the absence of Ct 3 gives an even higher conversion (95 cm), also has the advantage of not leaving any inhibiting residues in the reactor. Experiment 21 (
Example 2) pours out the liquid product from experiment 20,
All heavy iron powder remains at the bottom of the reactor, and new CC
Addition of l2 and (at%p6) shows that an excellent conversion of 94 h was obtained.

Another way to increase the conversion of this reaction without using iron powder is to increase the amount of ferric chloride and triethyl phosphite used. Experiment 22 doubled the normal usage of phosphite and increased the normal usage of ferric chloride to 1 t-
Even when multiplied by 4, the conversion rate increases slightly from the 43-48% achieved in experiments 5.6 and 7 to 68%. The use of iron powder-phosphite catalysts is not only cheaper but also has higher conversion rates (up to 95%).
).

In addition to increasing the t' of FeCL and (EtO), another alternative would be to increase the ethylene pressure, but to increase the conversion to 90% normal pressure? 4112 times, and the ferric chloride dragon needs to be increased by 4 times (Experiment 23). This method has the disadvantage that the yield drops from 95-96 inches to 90% despite requiring more expensive equipment and higher pressures. High conversion rates are desirable to reduce the cost of unreacted CCt4 by distillation and for other reasons.

Experiments 24 and 26 show that this reaction can be carried out at higher temperatures with fresh iron powder and phosphite to obtain 99% conversion in only 6.5 hours. However, the yield decreased slightly, and experiment 25 shows that the iron powder loses a significant amount of its activity when used a second time. Experiment 27 is 1
One way to compensate for the loss of iron activity upon reuse at 20 °C is to add a second portion to the reactor once the first portion of (Eto), p is consumed. ing.

In reactions that do not use ferric chloride but use fresh iron powder in the catalyst mixture, such as reactions 20, 24, and 26, there is initially little reaction until the mixture is heated for a period ranging from 20 minutes to 2 hours. The next one never happens.

If this is not desired, experiments 28 and 29
It has been shown that the presence of about 0.012 mole or more of L3 allows the reaction to start without the aforementioned delay upon heating.

The delay is believed to be due to the need to generate small amounts of iron salts from the iron powder, which act as intermediates in the initiation of the desired reaction. Run 30 shows that this small amount of added ferric chloride did not reduce the conversion when the reaction was repeated in the same reactor without solvent wash.

This is in contrast to the reduced conversion seen in Run 12, which used 10 times more ferric chloride in two consecutive reactions.

Experiment 31 shows that other alkyl phosphites used in the initiator mixture also work. This reaction was carried out similarly to Experiment 24, except that triethyl phosphite was replaced with tributyl phosphite. Similarly high yields and conversions were obtained with either phosphite ester.

Note that the temperature and pressure are considerably lower than in the Japanese literature. This shows the advantage of the invention. The above literature was primarily concerned with the initial rate of the reaction and therefore stopped the reaction after 1-2 hours, which is commercially impractical. Therefore, a direct parallel comparison with said literature is not possible.

Instead, the initiator of the above-mentioned document is used, but various experiments (
Experiments 1-7) t-do nari nen.

The foregoing description and examples are for illustrative purposes only and are not intended to limit the invention, which further includes other embodiments which are within the spirit of the invention and which will be obvious to those skilled in the art. I want to be understood as something.

Patent issuer Halo Kagenbu 5 Gukutsu Corporation, N patent agency agent

Claims (1)

[Claims] 1. By reacting carbon tetrachloride and ethylene in the presence of a catalyst containing a phosphite and an iron-containing material.
, 1,1,3-tetrachloropropane production method,
The above manufacturing method, characterized in that iron powder is used as the iron-containing material. 2. The method according to claim 1, wherein ferric chloride is further present. 3. The method according to claim 1, wherein the reaction is carried out in the substantial absence of oxygen. 4. The method according to claim 1, wherein the phosphite is triethyl phosphite. 5. The method according to claim 1, wherein the phosphite is tributyl phosphite. 6. At the end of the reaction, remove the liquid product from the reaction vessel to recover 1,1,1,3-tetrachloropropane, leaving solid iron powder in the reaction vessel, and additional phosphite, tetrachloride. The method according to claim 1, wherein the reaction is further carried out by adding carbon and ethylene. 7. The method according to claim 6, wherein the reaction vessel is washed with a solvent between successive reactions. 8. The method according to claim 7, wherein the solvent is methylene chloride. 9. The method according to claim 7, wherein the solvent is acetone. 10, about 70-140°C and about 25-500 psig
2. A method according to claim 1, wherein the reaction is carried out in the step of: 11. The method according to claim 1, wherein the iron powder is used in an excess of about 0.001 mole per mole of carbon tetrachloride. 12, the phosphite is triethyl phosphite,
The reaction was carried out in the substantial absence of oxygen at about 70-140°C for about 25°C.
A patent in which the initial feed rate of iron powder is approximately 0.001 molar excess per mole of carbon tetrachloride, and during continued runs additional iron powder is added to supplement the consumed iron. The method according to claim 6.