The method of liquid-phase chlorination of butadiene

 

(57) Abstract:

The invention relates to organic synthesis, in particular, to obtain a mixture WITH4chlorohydrocarbons predecessors jordanovic monomers for the synthesis of rubber. The main products in the mixture are 3,4-dichlorobutene-1,1,4-dichlorobutene-1, three - and tetrachlorobutane. Continuous liquid-phase chlorination of butadiene lead by conducting the reaction at boiling of the reaction mixture in the environment ethyl chloride containing 6 to 9 wt.% products of the chlorination of butadiene. The process is carried out either without a catalyst or with the use as catalyst of nitrogen-containing compounds, at a temperature of 14 - 30oC, when the molar ratio of butadiene : chlorine = 1.2 to 3 : 1. The catalyst is prepared by adding trialkylamine dissolved in ethyl chloride, the products of the chlorination of butadiene pre-or directly in the implementation process of the reaction. This results in a simpler technology and increases the yield of the final products. 2 C.p. f-crystals.

The invention relates to organic synthesis, and in particular, to the improvement of the method of liquid-phase chlorination of butadiene.

The products of the chlorination of butadiene are intermediate in the village of malament - and ozone-resistant, high resistance to aging, which is ensured by the presence in the polymer chain of the chlorine atom in a-position to the double bond. In this regard, all Jordanova hydrocarbons are particularly valuable.

The known method of chlorination of butadiene-1,3 liquid-phase chlorination of butadiene-1,3 (1) with chlorine in a solvent (CCI4, CHCl3, di-, tri - and tetrachlorethane, C4H8Cl2C6H6, PhCl, PhNO2C6H11C7H16, cyclohexane and so on) in the presence of 0.1-5% (by weight of the solvent sulphur or substances containing sulphur (CS2, Na2S, CaS, Na2S2O3H2, thiophene, mercaptans)) at a temperature of from 20 to 50oC, is obtained without high-boiling impurities dichlorobutene, yield 90% /Japan patent 19564, 1967/.

The disadvantage of this method is:

- the use of high-boiling solvents, the allocation of which at elevated temperatures leads to the formation of resinous products, polluting the distillation trichlorobutene and tetrachlorobutane that can be used to obtain valuable dichlorobutane;

- the complexity of the used catalytic systems.

Also known is a method of obtaining dichlorobutene by the chlorination of butadiene chlorine in prisutstvie the adiabatic mode at a molar ratio of butadiene and chlorine 1-3 : 1, and carbon tetrachloride take in quantity 4-8 mol per 1 mol of butadiene.

The disadvantage of this method is the use of high-boiling solvent, as well as strict temperature conditions for the reaction /patent of USSR 1022960, 1983/.

There is also known a method of liquid-phase chlorination of 1,3-butadiene from a mixture of 3,4-dichlorobutene - 1 and TRANS - 1,4-dichlorobutene - 2, comprising contacting 1,3-butadiene and elemental chlorine in a solvent, in an atmosphere essentially devoid of oxygen, in the presence of a chlorination catalyst, at 25-100oC and at a pressure sufficient to provide the resulting reaction mixture boiling point not lower than about 25-100oC when the mass ratio of the solvent and dichlorobutene 2.5 to 100 : 1, the separation of unreacted 1,3-butadiene and solvent from dichlorobutenes and removing dichlorobutenes, and the chlorination is performed in a cooled evaporation reactor, and the solvent is selected from the group consisting of butane, pentane or fluorinated hydrocarbons of the General formula

< / BR>
where

R is independently hydrogen, fluorine, chlorine or bromine;

R' is hydrogen;

R" is independently fluorine, chlorine or bromine;

m and n = 0 - 3.

The pace is our 1,3-butadiene and the solvent is returned to the reactor.

The disadvantage of this method is to conduct the chlorination under pressure, which significantly complicates the technological process /patent of Russia 2051892, 10.01.96/.

The closest and declared to the technical essence and the achieved effect is the chlorination of butadiene under isothermal conditions at a temperature of 40-60oC and a pressure of 4-5 bar, using as a low-boiling solvents such as butane, pentane, POLYHALOGENATED formula where R = H; R", R' is F, Cl, Br, m, and n = 0-3, end group, CH3or trihalomethyl.

As catalysts for use trialkylamine or phosphines, diallylsulfide or trialkylsilyl chloride in the amount of 20-200 million-1. For inhibition of radical processes apply tert-butylpyrocatechol, phenyl-naphtylamine, fentazin or sulfur to the amount of 20-80 million-1. Ratio of 3.4 : 1,4 HCD: the solvent is 1:2 - 11 /better 1:3 - 6/. The reaction is as follows. In cylindrical Nickel reactor with a height of 23 cm and a diameter of 1.8 cm skip a continuous flow of Cl2with a speed of 0.17 g/C and a mixture of butadiene (0.21 g/s) F2ClCCClF2(the boiling point of the 4oC, the molar ratio of butadiene : chlorine is 1 - 4 : 1) add a solution of phenyl -- and 4.5 ATM, selecting from the cube to the distillation of a mixture of butadiene, 3,4, and 1.4 dichlorobutene (DHB), the solvent and the formed products deeper chlorination.

The composition of the distillate:

3,4-DHB-46 wt.%

TRANS-1,4-DHB-47 wt.%

CIS - 1 wt.%

Trichlorobutene - 1.9 wt.%

Tetrachlorobutane - 4.2 wt.%

Monochlorotoluene - 0.5 wt.%

The disadvantage of this method is the use of fairly complex catalytic systems, complex technological performance of the equipment /U.S. patent 5077443, 1991/.

Carrying out the process at elevated temperature and pressure with the use of gaseous solvents and reagents in fact requires the same equipment as in gas-phase chlorination of butadiene.

The disadvantage is the use of ozone-dangerous freons, which according to the Montreal agreement on the protection of the ozone layer of the Earth is not recommended for commercial use.

The aim of the invention is the improvement of the method of liquid-phase chlorination of butadiene by conducting the reaction at boiling of the reaction mixture in the environment ethyl chloride containing 6-9% of the products of the chlorination of butadiene at a temperature of 14-30oC (advantages is risotti nitrogen-containing compounds mainly trialkyl-1-harbutt-2-yl-ammonium chloride or critically ammonium chloride with o chlorinated products of butadiene from a cube reactor without ethyl chloride or the content of 30-50% by the products of the chlorination of butadiene.

The method consists in the following. In a tubular reactor filled with a nozzle, placed ethyl chloride containing 6-9% of the products of the chlorination of butadiene, and in the lower part of the reactor served estimated number of butadiene and chlorine. Boiling ethyl chloride (18-22)oC with unreacted butadiene (the process is conducted at full depletion of chlorine fed to the adsorber with an alkaline reagent and then cooled in a brine refrigerator and a collector, where the pump-dispenser chilled ethyl chloride with dissolved butadiene returned to the middle part of the reactor. The accumulation in the reactor products of the chlorination of butadiene more than 9% they spontaneously gather in the lower part of the reactor, where no ethyl chloride, or with a small amount directed to the collection. In the absence of a catalyst outlet dichlorobutenes, when the molar ratio of butadiene : chlorine equal to 2:1, is 70-75% (the ratio of 3,4-DHB:1,4-DHB = 1:1), the rest of trichlorobutene and tetrachlorobutane. In the presence of 0.005 to 0.05% (mainly 0,008%) to chloride ethyl trialkyl-1-harbutt-2-yl-ammonium chloride, obtained by adding the corresponding trialkylamines in the products of the chlorination of butadiene, or critically ammonium harm-ethyl, the return of the cooled collection in the reactor.

The developed technology of liquid-phase chlorination of butadiene in comparison with the Prototype and other cited works has the following advantages:

simple technological process, under mild reaction conditions and obtain the desired products without solvent or with a small content;

- use as a low-boiling solvent (boiling point of 12.8oC), legkorastvorimah ethyl chloride, which is ozone friendly product;

- the use of catalysts, synthesized from the products of chlorination of butadiene (mainly of 1,4-dichlorobutene-2) adding to the mixture of the products of the chlorination of butadiene relevant trialkylamines that does not require installation of special site preparation of catalysts;

- the possibility of obtaining products of the chlorination of butadiene in a wide range of selectivity, providing high output dichlorobutenes and trichloroethanol and tetrachlorobutane predecessors remote 2,3-dichlorobutadiene;

- low consumption of the process.

The method is illustrated in the following primeralinea nozzle and is equipped with three nozzles in the lower part of the reactor (low to output products of the chlorination of butadiene, the average for the supply of butadiene, and the third is located 2 cm above the average for entering chlorine) and fitting in the middle part of the reactor to enter recirculated ethyl chloride, is placed 75 grams of ethyl chloride containing 0,008 wt.% triethyl-1-harbutt-2-yl - ammonium chloride or critically ammonium chloride.

Then in the corresponding fitting serves 0,624 g/min of styrene and 0.273 g/min of chlorine (the molar ratio of butadiene : chlorine is 3 : 1). The temperature in the reactor rises to 18-20oC and ethyl chloride, wikipedi from the upper part of the reactor together with unreacted butadiene, through the nozzle head is sent to the absorber filled with crystalline NaOH, and then goes in the fridge cooled brine.

Condensed ethyl chloride together with dissolved butadiene is collected in a cooled receiver, where the pump is dosing the mixture is fed into the middle portion of the reactor. Previously in the receiver dissolve 0,008 wt.% to ethyl chloride catalyst. Sustainable mode of chlorination occurs after 15-20 minutes, when ethyl chloride is accumulated 6-9 wt.% products of the chlorination of butadiene, and they spontaneously begin to accumulate at the bottom of the reactor, where in composition:

1. 3,4 - DHB - 69 wt.%

2. TRANS.-1,4-DHB - 18 wt.%

3. CIS -. -1,4-DHB - 3 wt.%

4. Trichlorobutene to 3.8 wt.%

5. Tetrachlorobutane - 5.4 wt.%

6. Monochlorotoluene to 0.8 wt.%.

Example 2.

In the conditions of example No. 1 of the chlorination was carried out in the absence of catalyst, feeding butadiene speed 0,436 g/min, chlorine 0,196 g/min Obtained 100 g of a mixture of chlorination products of composition:

1. 3,4 - DHB - 36 wt.%

2. TRANS.-1,4-DHB - 34 wt.%

3. CIS -. -1,4-DHB - 1.4 wt.%

4. Trichlorobutene - 9.2 wt.%

5. Tetrachlorobutane - 18 wt.%

6. Monochlorotoluene - 1.4 wt.%.

Example 3

In the conditions of example No. 2, the accumulation of chloride in the ethyl 6-9% of the products of the chlorination of butadiene, together with recycled ethyl chloride in the reactor serves triethylamine in an amount of 0.1% to the solvent. After the chlorination process (1-1 .5 hours) on a sustainable mode of supply of butadiene and chlorine increase accordingly to 0,624 g/min and 0.273 g/min, respectively. For 5 hours the reactor was obtained 120 g of a mixture of products of composition:

1. 3,4 - DHB - 68 wt.%

2. TRANS.-1,4-DHB - 20 wt.%

3. CIS -. -1,4-DHB - 3 wt.%

4. Trichlorobutene - 3 wt.%

5. Tetrachlorobutane - 6 wt.%

6. Monochlorotoluene - 1 wt.%.

Example 4
you're reactor received 132 g of a mixture of products of composition:

1. 3,4 - DHB - 62 wt.%

2. TRANS.-1,4-DHB - 25 wt.%

3. CIS -. -1,4-DHB - 1 wt.%

4. Trichlorobutene - 5.1 wt.%

5. Tetrachlorobutane - 6.2 wt.%

6. Monochlorotoluene - 0.7 wt.%.

Example N 5

In the conditions of example No. 1 molar ratio supplied butadiene and chlorine is 1.2:1 at a feed rate 0.124 g/min and 0,136 g/min, respectively. 5 hours of reactor operation received 71 g of a mixture of the composition:

1. 3,4 - DHB - 57 wt.%

2. TRANS.-1,4-DHB - 26 wt.%

3. CIS -. -1,4-DHB - 2 wt.%

4. Trichlorobutene - 2.8 wt.%

5. Tetrachlorobutane - 12 wt.%

6. Monochlorotoluene - 0.2 wt.%

Example N 7

In the conditions of example No. 1, the number of triethyl-1-harbutt-2-yl-ammonium chloride ranges from 0.005% to ethyl chloride.

For 5 hours received 104 g of a mixture of products of composition:

1. 3,4 - DHB - 45 wt.%

2. TRANS.-1,4-DHB is 30.5 wt.%

3. CIS -. -1,4-DHB - 1.5 wt.%

4. Trichlorobutene - 6 wt.%

5. Tetrachlorobutane - 16 wt.%

6. Monochlorotoluene - 1 wt.%

Example N 8

In 500 g of ethyl chloride was added 0.08 g of triethylamine and 0.06 g of allyl chloride. The mixture was stirred for at least 1 hour and used as a solvent chlorination of butadiene under the conditions of example No. 1.

5 hours of reactor operation received 131 g dichlormethane - 3 wt.%

5. Tetrachlorobutane - 6 wt.%

6. Monochlorotoluene - 1 wt.%.

1. The method of liquid-phase chlorination of butadiene chlorine in halodurans solvent at boiling of the reaction mixture, wherein the process is conducted in an environment ethyl chloride containing 6 to 9 wt.%, mainly 7 wt.%, products of the chlorination of butadiene at a temperature of 14 - 30oC, mostly 18 - 22oC, when the molar ratio of butadiene : chlorine, equal to 1.2 - 3 : 1, and the process is conducted recycle ethyl chloride, with the output products of the chlorination of butadiene from a cube reactor in the absence of ethyl chloride or content of 30 to 50 wt.%.

2. The method according to p. 1, wherein the process is conducted in the presence of nitrogen-containing catalyst selected from triethyl - or tributyl-1-harbutt-2-yl-ammonium chloride or critically ammonium chloride, taken in an amount of 0.005 to 0.05 wt.% in the calculation of the chloride ethyl, mainly in the number 0,008 wt.%.

3. The method according to p. 2, characterized in that the catalyst is obtained by adding the products of the chlorination of butadiene, composed mainly of 1,4-dichlorobutene-2, or allyl chloride dissolved in ethyl chloride, the corresponding three is

 

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