DE1543084C3 - Process for the production of chlorinated hydrocarbons - Google Patents

Description

Patent claims:

1. Process for the production of chlorinated hydrocarbons by means of chlorination in the presence of ionizing radiation, characterized in that chlorine gas is used continuously introduces into a conversion zone which is under high energy ionizing radiation, and there with saturated aliphatic ones present in the reaction zone in the gaseous or liquid phase or cycloaliphatic hydrocarbons or partially chlorinated derivatives of these compounds implements.

2. The method according to claim 1, characterized in that there is used as organic starting materials saturated aliphatic or cycloaliphatic hydrocarbons used, which have a low Amount of chlorinated saturated aliphatic or cycloaliphatic hydrocarbons added is.

3. The method according to claim 1, characterized in that one is saturated or aliphatic cycloaliphatic hydrocarbons in the gaseous state together with chlorine gas in the reaction zone introduces.

4. The method according to claim 3, characterized in that one is saturated or aliphatic cycloaliphatic hydrocarbons in the gaseous state together with chlorine gas in the Introduces reaction zone in which already chlorinated saturated aliphatic or cycloaliphatic Hydrocarbons are present.

35

The object of the invention is to ensure the effective formation of chlorinated or more highly chlorinated hydrocarbons to enable.

In Journal of Physical Chemistry, 68 (1964), p. 647, radiation-influenced (cobalt-60-γ-rays) chlorination of toluene described by tin chloride. In the experiment described, the starting materials were placed in a vessel, which was then exposed to radiation in the sealed state. The end products obtained included m- and p-chlorotoluene and o-chlorotoluene.

The stated object is achieved by the method defined in the preceding claims.

The influence of ionizing radiation on chlorination reactions is known (from Houben-Weyl, Methods derorganic chemistry, 4th edition, 1962, vol. V / 3, p. 523, last paragraph, to p. 524, paragraph 1). Also it is known that, because of the high penetrating power of these rays, the reactions also occur in closed metal vessels can be carried out. In contrast, it is found in the invention However, it is surprising that when the chlorine gas is continuously fed into the reaction zone, which is under high energy ionizing radiation, chain reactions of saturated hydrocarbons and the partially chlorinated derivatives with chlorine, which lead to chlorinated or higher chlorinated Lead hydrocarbons, are excited and the reactions can be sustained.

Under the action of the radiation, chlorine radicals are formed from the continuously supplied chlorine and hydrocarbon radicals from the hydrocarbon or the partially chlorinated hydrocarbon, which then react with one another before dimers can form. According to the known facts, it is assumed that the ionizing radiation breaks C - H and C - Cl bonds, so that radicals are formed. It is assumed that the following reactions of a C _n H _m Cl _p compound with chlorine occur under irradiation, where η is an integer and at least 1, ρ is an integer or zero and m + ρ = 2n + 2 .

.C ₁₁ H _1n Cl, -, + .Cl

.H

C _n H _n ^ ₁ CL ₊₁ + .Cl (2)

The reactions 1, Γ and 2 only occur under ionizing radiation and are caused by temperature or pressure is not affected. As soon as chlorine radicals are formed, the chlorination proceeds while the following chain reactions occur:

.Cl + C _n H _7n CL

.C _n H _n ^ ₁ Cl ₁ , + Cl ₂ > C _n H _n ^ ₁ CL ₊₁ + .Cl (4)

These chain reactions take place very quickly and are caused by the addition of chlorine gas into the Maintain the reaction system. The yield of more highly chlorinated hydrogen increases with the feed rate of the chlorine gas.

It was also found that the original presence of chlorinated hydrocarbon favorably influences the reaction between chlorine and hydrocarbon in the reaction mixture. the chlorinated hydrocarbons are decomposed first and with high efficiency, as in the Equations 1, Γ and 2 are expressed, and chlorine radicals are formed, which with the Hydrocarbon RH react as follows:

RH + .Cl
.R + Cl ₂

.R + HCl
RCl + .CI

In this chain reaction, the hydrocarbon is chlorinated with great yield.

It has also been found that further chlorination of relatively highly chlorinated hydrocarbons is possible under high energy radiation. Higher chlorinated hydrocarbons have more electrons than less highly chlorinated hydrocarbons, and the absorption of high energy radiation is at them higher. The more highly chlorinated hydrocarbons are used in reactions 1, Γ and 2 decomposed by radiation in an analogous manner, and the following chain reactions occur:

C _n H ^ Cl, +; - * .C _n H ^ CIp ₊₁ -, + .Cl (7)

C _n H _n -J ₁ CIp ₊₁₁ - * .C "H _m _ ^ ₊₁₁ CIp ₊ " + .H (7 ')

.Cl + C _n H _n ^ CL ₊₃ - .C "H _m _ _{(a + u} Clp _{+ a} + HCl

(8th)
• C _n H _m _ _{(a + u} CI _{p + CI} + ■ Cl ₂

->. C "H _m _ _{(a + 1)} Clp _{+ I + 1} + .Cl (9)

3 4

Highly chlorinated hydrocarbons are varied in good chlorine, a preferred one being chlorinated

Yield obtained. Chlorination can be synthesized in a similar hydrocarbon. Since chlorinating

Extent is through photochemical processes or through the hydrocarbon continuous through the reaction

catalytic reactions not possible. arises, it is not necessary to do so after beginning

Alicyclic hydrocarbons proceed to feed similar 5 to the reaction continuously.

Reactions if they are continuously fed in. As organic starting materials, for example

tem chlorine under ionizing radiation of high energy methane, ethane, propane, butane, pentane, hexane,

react. Heptane, octane, nonane, decane, undecane, dodecane

In the method according to the invention, the loading and cyclobutane, cyclopentane, cyclohexane, cyclo-

spoken reaction by the reaction of the reaction io heptane, cyclooctane or decahydronaphthalene

Components from the radiation absorbed energy are used.

initiated, and therefore any type of ionic radiation can be used when explaining the method according to the invention.
Sufficient energy to penetrate into the reaction system.
gen. The expression »ionizing radiation of high i ₅ Example!
Energy "or simply" ionizing radiation ", such as 99 g (1 mol) of 1,2-dichloroethane in a gas cylinder used in the following, refers to electromagnetic radiation with a short wavelength of 2.8 cm inside diameter and 50 cm length Cobalt-60 gamma radiation source of such as X-rays or gamma rays, further exposed to 10 kilocurie at a distance of 20 cm, rays of charged particles, which at high 20 which provides a radiation of 1.2 · 10 ⁵ rad / h. Chlorine move speed, like electrons, beta part- was at a speed of 250 ml (normal, protons, deuterons, alpha-particles and pressure and temperature) per minute and a temperature } nuclear fission particles, still rays new temperature of 30 ± 5 ° C introduced into the reaction vessel, neutral particles, such as fast neutrons, slow neutrons. With the entry of chlorine, the chlorination occurred as neutrons or thermal neutrons. Such ionization continues. After 3 hours, the vessel was removed from the high energy radiation can by radioiso radiation source, and the reaction product topen, particle accelerator and nuclear fission reac- was analyzed by gas chromatography,
gates are generated. The reaction product was liquid and weighed 154 g.

All saturated hydrocarbons and partially saturated - the following components were determined:

th hydrocarbons are for the method according to 30. . . _T. ,. .. , o per cent

of the invention if it is used in the reaction j'i'f ", ¹ " ^c ff, "f. ^, Γ«

, a- ■ j γ- · · j r> · 4.1 1,1,1,2-tetrachlorathane 25.0

phase are liquid or gaseous. The generated chlo- ₁ \ V- _Tetrach i _orethane 49 2

ured hydrocarbons can be solid, so that Μ, ^ - ietracnioratnan γ, ι

j τ,, ... , ι χτ · j ui ι · ι. * Pentachlorathane 17, ö

they from the reaction mixture as a precipitate easily _Η ι, ι - _{th n} s

are separable, or liquid, so that they can be separated by a 35 nexacnioratnan -u, 3

Distillation can be separated, or gaseous The gas flowing out of the reaction vessel

mig, so that it was collected in alkaline solution by distillation at low and ana-

Temperatures are separable. lysed. It contained

It is not necessary to use high purity chlorine, -,.,. «. , -, _o >,,

salary to use; the chlorine gas should, however, release ₄ o hydrogen chloride 1.78 months

of oxygen or other coarse impurities (unreacted) chlorine gas 0.04 mol

If a high yield of the desired products is to be obtained, the reaction described was to be obtained with variable products. Furthermore, it is not necessary to remove the reaction vessel from the radiation, to use purified hydrocarbons, and indeed the removal was the. There will be no noticeable exposure time, such as 45 between 10 and 200 cm. In the photochemical process described, this corresponds to a dose of between 3 · 10 ⁵ to 1 · 10 ³ rad / h. It was ascertained to occur. found that at least 1 · 10 ³ rad / h is necessary

The reaction takes place at room temperature or is to initiate the reaction and the chain reaction

quickly decreases even at low temperatures. To maintain the tion. The feed speed

To keep reaction components gaseous or liquid, 50% of the chlorine was in the range of 100 to 1200 ml

if necessary in this regard, the response per minute is varied; that is, it got about 0.005

preferably carried out at higher temperatures. to 0.05 moles per minute and per mole of dichloroethane

The radiation of high energy does not make the intended use. It was found that the yield with

manure of special substances of the process equipment of necessity increases the feed rate of the chlorine, whereby

agile, and the reaction can take place at any temperature 55 but a higher dose rate is needed; if

be performed. This is one of the most important a larger amount of dichloroethane to be chlorinated

Features of the invention. should feed speed and radiation

The method according to the invention can either be increased in proportion to the dose,

intermittently or continuously through- B "'1 2

leads to be. In the continuous process, 60 e 1 s ρ 1

wise are hydrocarbons, chlorinated carbon 99 g (1 mol) 1,2-dichloroethane were in an email

hydrogen and chlorine together in a mixture in the lated mild steel vessel of the same dimensions as

Reaction vessel passed, or these three components brought the reaction vessel according to Example 1. It was

are conveyed individually into the reaction vessel, in the same conditions as in Example 1

which will only maintain high energy radiation on the react 65 during chlorination

system acts. When the mixing speed- the pressure in the vessel was reduced to 5 kg / cm ² and the

ity or the velocity of the hydrocarbon temperature is kept at 100 ± 5 ° C. Chlorine gas was

and / or the chlorinated hydrocarbon and the at a rate of 200 ml (normal

temperature, normal pressure) per minute for two hours, then the reaction product was analyzed. The reaction product was liquid and weighed 130 g.

Its composition was as follows:

■ mole percent

Dichloroethane 14

1,1,2-trichloroethane 60

1,1,1,2-tetrachloroethane 11

1,1,2,2-tetrachloroethane 15

In total, the following other substances were also collected:

Hydrogen chloride 1.05 moles

(unreacted) chlorine 0.01 mol ' ⁵

The same procedure was repeated with alternating pressures and temperatures, and it became. found that this has no significant effect on the chlorination.

Example 3

The vessel used in Example 2 was 113g (1 mole) 1,2-dichloropropane filled and at a distance arranged by 20 cm of the aforementioned radiation source. It was coming at a speed of 250 ml / min and 30 ± 2 ° C chlorine gas supplied under atmospheric pressure. After 2 hours 130 g of liquid reaction product were obtained. The composition of the reaction product was

^f0l 8 ^end: mole percent

1,2,2-trichloropropane 39.2

1,1,2-trichloropropane 17.7

1,2,3-trichloropropane 25.0

1,1,2,2-tetrachloropropane 7.2

1,2,2,3-tetrachloropropane 7.5

1,1,2,3-tetrachloropropane 0.2

In total, the following other substances were also collected:

Hydrogen chloride 1.9 moles

(unreacted) chlorine 0.04 mol

Example 4

35

45

The experiment according to Example 3 was repeated with a pressure of 10 kg / cm ² and chlorine gas was fed in at a rate of 750 ml (normal temperature and pressure) per minute. The total amount of liquid product was 156 g and the density was 1.49. The main ingredient of the product was chloropropane with an average of 3.8 chlorine atoms per molecule. 1.78 mol of HCl were obtained, and 0.02 mol of chlorine gas remained, which means that there was no reaction.

Example 5

20 g of paraffin (melting point 50 to 52 ° C), dissolved in 180 g of carbon tetrachloride, were in the example 1 introduced the vessel described. The paraffin was made under the conditions described in Example 1 chlorinated, with chlorine gas at a rate of 200 ml / min at 30 ± 2 ° C during 2.5 hours was passed. 204 g of reaction products were obtained. After the carbon tetrachloride Was distilled off under reduced pressure, 58 g of solid remained, which is a Had a density of 2.73. The chlorine content of the solid was 67.7 percent by weight. There were 1.12 moles HCl and 0.09 mol of chlorine obtained.

Example 6

84 g of cyclohexane were chlorinated in the apparatus described in Example 2. The reaction vessel was at a distance of 40 cm from the radiation source, which consisted of 10 kilocuries of cobalt-60 duration. Chlorine gas was injected at a rate of 200 ml / min at 30 ± 2 ° C and under atmospheric Pressure passed through the cyclohexane. After one hour, 97 g of liquid reaction product were obtained receive. The analysis of the end product brought the following results proportionally:

Mole percent

Cyclohexane

Monochlorocyclohexane
Dichlorocyclohexane ...

49
46

In total, the following other substances were also collected:

Hydrogen chloride 0.53 mole

Chlorine gas 0.01 mole

Example 7

72 g of n-pentane were chlorinated in the apparatus described in Example 1. The jar was at a distance 20 cm from the radiation source 10-kilocurie cobalt-60 removed, and the chlorine gas was at a rate of 100 ml / min under atmospheric pressure through the boiling at about 36 ° C n-pentane passed for two hours. 84.5 g of liquid reaction product were obtained, its Composition was:

Mole percent

40

n-pentane ... "

Monochloropentane
Dichloropentane ...

55

42

0.46 moles of hydrogen chloride and 0.02 moles of chlorine were collected.

Example 8

A reaction vessel made of nickel with a diameter of 10 cm and a depth of 1 cm was fitted with a provided with a thin nickel film window of 0.01 mm thickness and surrounded by a water jacket. There were Put 25 g paraffin (melting point 50 to 52 ° C) into this vessel and liquid at about 90 + 2 ° C held by running hot water through the jacket. It was getting chlorine gas at a rate of 100 ml / min was passed into the vessel, and the reaction system was activated with an electron beam irradiated from a distance of 50 cm, which is from a 2 MeV van de Graff electron accelerator came from. The electron beam flow was directed into the vessel through the window mentioned. After 100 minutes Irradiation gave 41 g of the reaction product. Their density was 1.15 and the analysis showed that the product contained 39 weight percent chlorine.

Example 9

The vessel used in Example 2 was filled with 93 g (1 mol) of 2-chlorobutane, and the vessel was in at a distance of 30 cm from the radiation source described above. It became chlorine gas

at a rate of 100 ml (normal pressure regulated so that the internal pressure in the vessel at 5 kg / cm ² and temperature) per minute was fed into the vessel. As soon as methane and chlorine were introduced into the vessel and the temperature was on 50 ± 2 ° C, the pressure, the chlorination began immediately. Non-volatiles kept at 5 kg / cm ² . After 3 hours, the chlorination products were collected in the vessel, the vessel removed from the radiation source, and the hydrogen chloride generated and some of the volatile products obtained were analyzed. The reac- chlorination products arrived together with the ionization product was liquid and weighed 111 g. The specific unreacted gas mass through the safety valve fish weight was 1.09, and the main component in the cooled receiver filled with water and alkali was C ₄ H ₈₃₃ Cl ₁₆₇ . According to the gas chromatographic vessels. The hydrogen chloride and the unreacted analysis gave the product approximately 33 mole percent io chlorine were collected in the two unreacted monochlorobutane collecting devices, the identification of which was collected and analyzed quantitatively. The volatile isomers of the dichlorobutanes and trichloro reaction products obtained were in the first catch but pre-butane was difficult to carry out. direction and formed a lower layer.

Mole percent as methane and chlorine continuously in the vessel

Unreacted monochlorobutane ... 33 ¹⁵ ™ J at ^a rate of 90 ml per minute and

Mixture of higher chlorinated butanes 67 ²¹⁰ f P ^ro , ^ ™ ^ ^en V- ^S t ^ ^{to be fed}

the following results were obtained:

In total, the following additional substances were: The entire reaction product including the

collected: reaction products collected in the pressure vessel,

Hydrogen chloride 0.74 mole ^{20 the} carbon tetrachloride which from the beginning

ChIo as QQ _{05 Mo} jan was present, and the one in the catchment devices

'Product collected weighed 439 g. Of course,

B * ice pie 1 10 ^{th em} strength ^e of the volatiles to escape through the collecting device.

100 g (1 mol) of n-heptane was in Example 2 _{25 D} j _e analysis of the total reaction product and the

described apparatus chlorinated. The reaction vessel collected gases produced the following results:
was at a distance of 30 cm from the 10-kilogram

curie cobalt 60 radiation source. Chlorine carbon tetrachloride 2.29 moles

gas was at a rate of 100 ml of chloroform 0.53 mol

(Normal temperature and pressure) per minute through the ₃₀ methylene chloride 0.26 mol

n-heptane passed, and the temperature was adjusted to 0.02 mole methyl chloride

90 ± 2 ° C, the pressure kept at 5 kg / cm ² . According to hydrogen chloride 3.27 mol

3 hours the gas from the vessel was collected unreacted chlorine 0.10 mol

and analyzed, the reaction product was reacted unreacted methane

collects and weighed 122 g. The specific gravity was ₃₅ permeable

0.85, the main ingredient was C ₇ H ₁₅ J ₂ Cl ₀ ,,,,. According to this, 2 moles of carbon tetrachloride can be used as from

the gas chromatographic analysis indicated that the beginning was considered to be present in the pressure vessel

Reaction product will be about 36.5 mole percent unreacted.

n-heptane, the identification of the isomers of the produc- B e i s ρ i e 1 12

However, the ten chlorheptane and dichloroheptane was ₄₀ "~ _r ~.", _. ...., ... ""

difficult pressure vessel according to example 11 was with 308 g

(2 moles) of carbon tetrachloride charged, and that

ο percent vial was at a distance of 30 cm from the

Unreacted n-heptane 36.5 gamma ray source set up.

Mixture of chlorinated heptane 63.5 Liquefied natural gas with the following components:

In total, the following additional substances " _A. , Mol percent

Hydrogen chloride 0.75 mol

Chlorine gas 0.006 mole

Two are attached to a pressure vessel made of enamelled steel with an inside diameter of 4 cm and a depth of 50 cm tapped inlets are attached to the lower end and there becomes a water-cooled reflux condenser connected to the top of the vessel, this condenser with a safety valve or check valve is provided at the upper end. The vessel also comes with a Thermocouple thermometer and a pressure gauge. This jar was 309 g (2 moles) carbon tetrachloride filled and at a distance of 20 cm from the cobalt-60 gamma ray source set up and kept at 60 ° C. The gaseous methane and chlorine were released by the two Inlets introduced at the bottom of the jar. The safety valve or check valve was so

η-butane 31

Isobutane 13

⁵⁰ Pentane 5

was fed into the vessel through one of the two lower inlets at a rate of 100 ml (normal temperature and pressure) per minute, and ₅₅ chlorine was fed through the other inlet at a rate of 300 ml (normal pressure and temperature) per minute Minute introduced.

During the reaction the vessel was kept at 50 ° C and the safety valve or check valve in the upper part of the reflux condenser was kept open. After the above reaction ingredients were fed for 5 hours, a total of 500 g of the reaction product, the specific gravity of which was 1.48, was obtained.
65 The amount of the obtained hydrogen chloride was 3.66 mol and that of the unreacted chlorine gas was 0.10 mol. Unreacted liquefied natural gas was not detected in the outflowing gas.

409 644/243

Example 13

Five curved quartz tubes, each 0.6 cm in inner diameter and 50 cm in length, were placed in the Art a trumpet and a gas inlet was provided at each bend. This Set of tubes, with each tube arranged horizontally, were placed at a distance of 50 cm from the cobalt-60 gamma ray source. It methane was introduced into the set of tubes from the top end inlet and chlorine gas through these and the other inlets introduced at the four bends. When these reaction components are in the Set of pipes placed under the action of gamma rays found chlorination took place immediately, and the temperature of the pipes was over 200 ° C. The reason why the chlorine supply was made through five different inlets in the tube, in order to generate too rapid heat to avoid. With this method of supplying the chlorine, the pipe does not need anything else than through the Ambient air to be cooled. The gases discharged at the lower outlet of the set of tubes were collected and condensed by the processes already described.

As methane at a rate of 100 ml (normal temperature and pressure) per minute and Chlorine at a rate of 60 ml (normal temperature and pressure) per minute through each of the five inlets was fed, the continuously discharged and condensed product showed a specific one Weight of 1.5, which indicates that the reaction product is mainly from Consists of carbon tetrachloride and chloroform. Unreacted methane and chlorine were in the capture product not discovered.

Example 14

The experiment described in Example 13 was carried out with liquefied natural gas of the specified composition repeated. This time the set of pipes was at a distance of 30 cm from the Gamma ray source arranged.

Methane was at the top inlet at a rate of 100 ml (normal temperature pressure) per minute and chlorine at a rate of 50 ml (normal temperature pressure) per Minute, the chlorine was continued through the second inlet (inlet at the first knee) with a Speed of 100 ml (normal pressure and temperature) per minute and through the third Inlet (on the second knee) at a rate of 150 ml (normal temperature and pressure) per minute fed.

The condensed product had a specific gravity of 1.31, and unreacted natural gas and Chlorine gas was not detected underneath.

Claims (4)

Patent claims: 1. Process for the production of chlorinated hydrocarbons by means of chlorination in the presence of ionizing radiation, characterized in that chlorine gas is used continuously introduces into a conversion zone which is under high energy ionizing radiation, and there with saturated aliphatic ones present in the reaction zone in the gaseous or liquid phase or cycloaliphatic hydrocarbons or partially chlorinated derivatives of these compounds implements. 2. The method according to claim 1, characterized in that there is used as organic starting materials saturated aliphatic or cycloaliphatic hydrocarbons used, which have a low Amount of chlorinated saturated aliphatic or cycloaliphatic hydrocarbons added is. 3. The method according to claim 1, characterized in that one is saturated or aliphatic cycloaliphatic hydrocarbons in the gaseous state together with chlorine gas in the reaction zone introduces. 4. The method according to claim 3, characterized in that one is saturated or aliphatic cycloaliphatic hydrocarbons in the gaseous state together with chlorine gas in the Introduces reaction zone in which already chlorinated saturated aliphatic or cycloaliphatic Hydrocarbons are present. 35 The object of the invention is to ensure the effective formation of chlorinated or more highly chlorinated hydrocarbons to enable. In Journal of Physical Chemistry, 68 (1964), p. 647, there is radiation-influenced (cobalt-60-γ rays) chlorination of toluene described by tin chloride. In the experiment described, the starting materials were placed in a vessel, which was then exposed to radiation in the sealed state. The end products obtained included m- and p-chlorotoluene and o-chlorotoluene. The stated object is achieved by the method defined in the preceding claims. The influence of ionizing radiation on chlorination reactions is known (from Houben-Weyl, methods derorganic chemistry, 4th edition, 1962, vol. V / 3, p. 523, last paragraph, to p. 524, paragraph 1). Also it is known that, because of the high penetrating power of these rays, the reactions also occur in closed metal vessels can be carried out. In contrast, it is found in the invention However, it is surprising that when the chlorine gas is continuously fed into the reaction zone, which is under high energy ionizing radiation, chain reactions of saturated hydrocarbons and the partially chlorinated derivatives with chlorine, which lead to chlorinated or higher chlorinated Lead hydrocarbons, are excited and the reactions can be sustained. Under the action of the radiation, chlorine radicals are formed from the continuously supplied chlorine and hydrocarbon radicals from the hydrocarbon or the partially chlorinated hydrocarbon, which then react with one another before dimers can form. According to the known facts, it is assumed that the ionizing radiation breaks C - H and C - Cl bonds, so that radicals are formed. It is assumed that the following reactions of a C "H _m Cl _p compound with chlorine occur under irradiation, where η is an integer and at least 1, ρ is an integer or zero and m + ρ = 2n + 2 . C "H _m Cl _p
C "H _m Cl _p .H + Cl ₂ > C ₁ H ₁ -ICl, +, + -Cl (2) The reactions 1, Γ and 2 only occur under ionizing radiation and are caused by temperature or pressure is not affected. As soon as chlorine radicals are formed, the chlorination proceeds while the following chain reactions occur: .Cl C "H _m Cl _p + Cl ₂ - C _n H ^ ₁ CIp + HCl (3)
+ C _n H ₁ ^ ₁ CIp ₊₁ + .Cl (4) These chain reactions take place very quickly and are caused by the addition of chlorine gas into the Maintain the reaction system. The yield of more highly chlorinated hydrogen increases with the feed rate of the chlorine gas. It was also found that the original presence of chlorinated hydrocarbon favorably influences the reaction between chlorine and hydrocarbon in the reaction mixture. the chlorinated hydrocarbons are decomposed first and with high efficiency, as in the Equations 1, Γ and 2 are expressed, and chlorine radicals are formed, which with the Hydrocarbon RH react as follows: RH + .Cl
.R + Cl, .R + HCl RCl + .Cl In this chain reaction, the hydrocarbon is chlorinated with great yield. It has also been found that further chlorination of relatively highly chlorinated hydrocarbons is possible under high energy radiation. Higher chlorinated hydrocarbons have more electrons than less highly chlorinated hydrocarbons, and the absorption of high energy radiation is at them higher. The more highly chlorinated hydrocarbons are used in reactions 1, Γ and 2 decomposed by radiation in an analogous manner, and the following chain reactions occur: .-! + .Cl (7)
Cl, +. + .H (7 ')
_ _{((Z + 1)} Clp _{+ a} + HCl (8) .Cl + C _n H _n ^ ₁ CL Cl ₂ .C "H _m _ _{(It + 1)} Clp _{+ a + 1} + .Cl (9)