WO1991002708A1 - Methode d'isomerisation de 1,2-ethane dichlorique - Google Patents

Methode d'isomerisation de 1,2-ethane dichlorique Download PDF

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Publication number
WO1991002708A1
WO1991002708A1 PCT/US1989/003654 US8903654W WO9102708A1 WO 1991002708 A1 WO1991002708 A1 WO 1991002708A1 US 8903654 W US8903654 W US 8903654W WO 9102708 A1 WO9102708 A1 WO 9102708A1
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WO
WIPO (PCT)
Prior art keywords
free radical
radical initiator
dichloroethene
cas
isomerization
Prior art date
Application number
PCT/US1989/003654
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English (en)
Inventor
Earl M. Gorton
Original Assignee
Ppg Industries, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ppg Industries, Inc. filed Critical Ppg Industries, Inc.
Priority to PCT/US1989/003654 priority Critical patent/WO1991002708A1/fr
Publication of WO1991002708A1 publication Critical patent/WO1991002708A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation

Definitions

  • trans-1,2-dichloroethene [CAS 156-60-5] and cis-1,2-dichloroethene [CAS 156-59-2] are valuable compounds having a variety of uses. They may be used separately or together in various proportions as low temperature extraction solvents for heat sensitive substances, as solvent for the manufacture of rubber solutions, and as coolant in refrigeration plants. Each compound has been copolymerized with other ethylenically unsaturated monomers to form copolymer ⁇ .
  • 1,2-Dichlororethene [CAS 540-59-0] can be produced by direct chlorination of acetylene at about 40°C to about 80°C, by the reduction of 1,1,2,2-tetrachloroethane, by the pyrolytic deliydrochlorination of 1,1,2-trichloroethane, or as a by-product in the chlorination of chlorinated compounds.
  • the 1,2-dichloroethene comprises a mixture of the trans and cis isomers, the proportions of which depend upon the conditions of manufacture.
  • _trans-l,2-dichloroethene or a trans-rich mixture of the two stereoisomers is preferred.
  • Trans-1.2-dichloroethene is more reactive chemically than the cis-iso ⁇ ter ⁇ especially in 1,2-addition reactions. It also has a lower normal boiling point and a lower latent heat of vaporization than the cis-isomer. thereby favoring the trans-isomer or a irang-rich mixture for extractions where it is desired to recover the
  • the .trans-isomer also has a lower viscosity than the cJLs-isomer, so that less energy is required for pumping the trans-isomer or trans-rich mixture of the two stereoisomers.
  • £i ⁇ -l,2-dichloroethene or a cis-rich mixture of the two stereoisomers is preferred. Since the c_is.-ison.er has a lower melting point than the .trans-isomer, the cis-isomer or a cis-rich mixture is better suited for use as an indirect heat transfer medium in refrigeration systems operating at low temperatures. The solubility of the cis-isomer in water at 25°C is less than that of the trans-isomer. so that the £is-isomer or a cis-rich mixture of the stereoisomers is preferred for some extractions where an aqueous phase is present. The lower chemical activity of the cis-isomer is advantageous where chemical stability is desired.
  • the invention is a method comprising isomerizing one stereoisomer of 1,2-dichloroethene to the other stereoisomer of 1,2-dichloroethene in the liquid phase and in the presence of free radical initiator.
  • a preferred embodiment is a method comprising isomerizing cis-1.2-dichloroethene to trans-1.2-dichloroethene in the liquid phase and in the presence of free radical initiator.
  • the same free radical initiators can be used to promote the liquid phase somerization of i ⁇ ans-1,2-dichloroethene to cis-1.2-dichloroethene.
  • Another embodiment is a method comprising isomerizing trgns-1,2-dichloroethene to cis-1 «2-dichloroethene in the liquid phase and in the presence of free radical initiator.
  • One class of suitable organic free radical initiators 6 comprises the organic peroxygen-containing free radical initiators.
  • This class may be divided into a large number of subclasses, some of 8 which are as follows:
  • Peroxides exemplified by diethyl peroxide, di-tgrt-butyl 10 peroxide [CAS 110-05-4], n-butyl 4,4-bis(te t-butylperoxy)valerate, l,l-bis(te t-butylperoxy)-3,3,5-trimethylcyclohexane, bis-t£rt-butyl 12 peroxides of diisopropylbenzene, dicumyl peroxide [CAS-80-43-3] , 2,5-dimethyl-2,5-bis(te t-butylperoxy)hexane [CAS 78-63-7], and 14 2, ⁇ -dimethyl-2,5-bis(te t-butylperoxy)-3-hexyne [CAS 1068-27-5].
  • Hydroperoxides exemplified by methyl hydroperoxide, 16 tert-butyl hydroperoxide [CAS 75-91-2] , cumyl hydroperoxide [CAS 75-91-2] .
  • Ketone peroxides exemplified by methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, 22 2,4-pentanedione peroxide, the 1,2,4,5-tetraoxacyclohexanes, and the
  • Diacyl peroxides exemplified by diacetyl peroxide [CAS 32 110-22-5], dibenzoyl peroxide [CAS 94-36-0], dicaprylyl peroxide, bis(4-chlorobenzoyl) peroxide, didecanoyl peroxide, 34 bis(2,4-dichlorobenzoyl) peroxide [CAS 133-14-2], diisobutyryl peroxide [CAS 3437-84-1], diisononanoyl peroxide, dilauroyl peroxide [CAS 105-74-8], dipelargonyl peroxide, dipropionyl peroxide, and 2 bis(3-carboxylpropionyl) peroxide.
  • Peroxycarboxylic acids exemplified by peroxyacetic acid.
  • 4 Peroxyester ⁇ exemplified by tert-butyl peroxyacetate [CAS
  • Peroxycarbonates exemplified by te t-butylperoxy isopropyl 16 carbonate.
  • Peroxydicarbonates exemplified by diisopropyl 18 peroxydicarbonate [CAS 105-64-6], di-s ⁇ £-butyl peroxydicarbonate, di-n-propyl peroxydicarbonate [CAS 16066-38-9], di(2-ethylhexyl) 20 peroxydicarbonate, dicyclohexyl peroxydicarbonate [CAS 1561-49-5], and dicetyl peroxydicarbonate [CAS 26322-14-5].
  • Another class of suitable organic free radical initiators comprises the organic azo-nitrile initiators, of which there are 24 many. Examples of suitable azo-riitrile initiators include
  • the free radical initiator and the 1,2-dichloroethene are combined at a weight ratio of the free radical initiator to the 32 1,2-dichloroethene in the range of from about 5 parts per million parts (ppm) to about 2000 ppm. Frequently, the weight ratio is in 34 the range of from about 20 ppm to about 1500 ppm. From about 50 ppm to about 1000 ppm is preferred.
  • the liquid reaction mixture in which the isomerization 2 reaction is conducted may contain only 1,2-dichloroethene and free radical initiator or it may also contain other materials which do not 4 seriously interfere with the isomerization reaction.
  • the 1,2-dichloroethene should be present in more than a 6 trivial or inconsequential amount.
  • the 1,2-dichloroethene constitutes at least about 10 weight percent of the reaction mixture, 8 taken on an initiator-free basis. In many cases the
  • 1,2-dichloroethene constitutes at least about 50 weight percent of 10 the reaction mixture, taken on an initiator-free basis. Often the 1,2-dichloroethene constitutes at least about 70 weight percent of 12 the reaction mixture taken on an initiator-free basis. At least about 95 weight percent, taken on an initiator-free basis, is 14 preferred.
  • the reaction may be conducted batchwise, ⁇ emi-batchwise, 16 continuously, or semi-continuously.
  • the temperature of the reaction may vary considerably. 18 Usually, however, the temperature is in the range of from about 0°C to about 100°C. Often the temperature is in the range of from about 20 35 ⁇ C to about 70°C. From about 45 ⁇ C to about 60 ⁇ C is preferred.
  • the isomerization reaction is conveniently, but not 22 necessarily, conducted at reflux temperature.
  • the isomerization reaction is 24 usually conducted at about ambient atmospheric pressure or slightly above, although greater or lesser pressures may be used as desired.
  • the reflux temperature may be altered from the atmospheric reflux temperature by employing 28 pressures above or below ambient atmospheric pressure.
  • the reaction mixture may be distilled to 30 separate the trans-1.2-dichloroethene from the cis-1 -2-dichloroethene. This may be accomplished after the 32 isomerization reaction has been completed or while the isomerization reaction is being conducted. In the latter instance the desired 34 stereoisomer may be recovered while the other stereoisomer is returned to the reaction mixture for isomerization.
  • concentrations of the stereoisomers are prevented from approaching the equilibrium concentrations too closely thereby enhancing the overall rate of reaction and permitting essentially all of the undesired stereoisomer to be converted to the desired stereoisomer.
  • the invention is further described in conjunction with the following examples which are to be considered illustrative rather than limiting, and in which all parts are by weight and all percentages are percentages by weight unless otherwise specified.
  • Component Composition wt. percent trans-1,2-Dichloroethene 2-5 cis-1,2-Dichloroethene 50-55 Chloroform 6-8

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

On effectue l'isomérisation d'un stéréo-isomère de 1,2-éthane dichlorique avec l'autre stéréo-isomère en phase liquide et en présence d'un initiateur radical libre.
PCT/US1989/003654 1989-08-24 1989-08-24 Methode d'isomerisation de 1,2-ethane dichlorique WO1991002708A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US1989/003654 WO1991002708A1 (fr) 1989-08-24 1989-08-24 Methode d'isomerisation de 1,2-ethane dichlorique

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1989/003654 WO1991002708A1 (fr) 1989-08-24 1989-08-24 Methode d'isomerisation de 1,2-ethane dichlorique

Publications (1)

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WO1991002708A1 true WO1991002708A1 (fr) 1991-03-07

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005110954A1 (fr) * 2004-04-29 2005-11-24 Ppg Industries Ohio, Inc. Procede permettant de recuperer du trans-1,2-dichloroethene

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
Beilsteins Handbuch der organischen Chemie, EIII, Vol. 1, 1958 Friedrich Richter: "Chemisches Verhalten ", see page 652- page 653. *
Chemical Abstracts, vol. 104, no. 13, 31 March 1986, (Columbus,Ohio, US), Ike be Haruhiro et al: "Fumaric acid monoesters", see page 669, abstract 109049q, & Jpn. Kokai Tokkyo Koho JP-A-60 181 047. *
Chemical Abstracts, volume 58, no., 1963, (Columbus, Ohio, US), E.B. Milo vskaya et al : "Trans isomerization of dimethyl maleate under the influence of free radicals ", see, column 445e, & Zh. Obshch. Khim. 1962, 32(), 621- 6 (1962). *
Chemical Abstracts, volume 86, no. 15, 11 April 1977, (Columbus, Ohio, US), Flid R.M. et al : "Cis- and trans-1,2-dichloroethylene ", see page 453, abstract 105921e, & SU-A-541 832A, 1905. *
J. Am. Chem. Soc., Vol. 59, June 1937 M.S. Kharasch et al: "Cis-trans isomerization by bromine atoms ", see page 1155. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005110954A1 (fr) * 2004-04-29 2005-11-24 Ppg Industries Ohio, Inc. Procede permettant de recuperer du trans-1,2-dichloroethene
US7268262B2 (en) 2004-04-29 2007-09-11 Ppg Industries Ohio, Inc. Method for recovering trans-1,2-dichloroethene

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