US3449412A - Continuous production of 1,4,5,6,7,7-hexachlorobicyclo - (2,2,1) - 5 - heptene - 2,3-dicarboxylic acid - Google Patents

Continuous production of 1,4,5,6,7,7-hexachlorobicyclo - (2,2,1) - 5 - heptene - 2,3-dicarboxylic acid Download PDF

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US3449412A
US3449412A US549352A US3449412DA US3449412A US 3449412 A US3449412 A US 3449412A US 549352 A US549352 A US 549352A US 3449412D A US3449412D A US 3449412DA US 3449412 A US3449412 A US 3449412A
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heptene
hexachlorobicyclo
dicarboxylic acid
solution
reaction
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US549352A
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Horst Goelz
Hubert Suter
Albert Palm
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C61/16—Unsaturated compounds
    • C07C61/28—Unsaturated compounds polycyclic

Definitions

  • 1,4,5,6,7,7-hexachlorobicyclo-[2,2,1] 5 heptene 2,3- dicarboxylic acid has hitherto been the most valuable acid component for the production of self-extinguishing polyester resins.
  • very high purity requirements are placed on the 1,4,5,6,7, 7-hexachlorobicyclo-[2,2,11-5-heptene 2,3 dicarboxylic acid.
  • the solvents may be hydrocarbons, for xylene, toluene or hexane, or chlorinated hydrocarbons, for example mouene or hexane, or chlorinated hydrocarbons, for example monochlorobenzene, o-dichlorobenzene, m-dichlorobenzene and carbon tetrachloride. Since the diene synthesis proceeds exothermally, the process is often carried out with vapor cooling. Using solvents necessitates recycling the assistant in the industrial form of the process. This assistant then in turn has to be separately purified.
  • chlorohydrocarbons Quite apart from the circulation of the solvent, all other chlorohydrocarbons have to be removed from the product, both unreacted hexachlorocyclopentadiene and the byproducts, for example hexachlorocyclopentene. These chlorohydrocarbons not only cause detrimental discoloration or further decomposition products, but they are also skin irritants and produce a type of dermatitis.
  • the object of the present invention is a process for the continuous production of pure 1,4,5,6,7,7-hexachlorobicyclo-[2,2,1]-5-heptene-2,3-dicarboxylic acid from hexachlorocyclopentadiene and maleic anhydride in which the reaction and the purification of the product of the process can be carried out far more simply than in the prior art methods, which may be carried out on a large scale in a simple way and which requires only small expenditure on protective measures against the physiological effects of the chlorohydrocarbons.
  • Hexachlorocyclopentadiene and maleic anhydride are usually supplied to the reactor in a molar ratio of from 08:13 to 1320.8, preferably in a molar ratio of from 0.9:l.l to l.l:0.9.
  • the reaction temperature and the residence time are interdependent. At temperatures only slightly above 120 C., residence times of up to seven hours are required, whereas at reaction temperatures of 200 C., a residence time of two hours is sufficient. It is preferred to use reaction temperatures of 135 to 180 C. and residence times of three to five hours.
  • the reactor may be one or more stirred vessels, for example in cascade arrangement.
  • the process may however be carried out in reaction tubes. In this case the preferred tubes are those whose diameter/ length ratio is from 1:30 to 1:100, particularly from 1:50 to 1:60.
  • a stirrer preferably rotating at slow speed, may also be used in the reaction tube to mix the reaction materials.
  • the process is usually carried out at atmospheric pressure; it may however also be carried out at subatmospheric pressure, for example down to 20 mm. Hg, or superatmospheric pressure, for example up to atmospheres gauge.
  • Nitrogen, carbon dioxide, rare gases or methane are suitable for example as the inert gas atmosphere in the reactor.
  • reaction mixture After the reaction mixture has left the reactor it is passed at atmospheric or slightly subatmospheric pressure, for example at 300 mm. Hg, or at superatmospheric pressure, for example at 2 atmospheres gauge, into Water at a temperature of more than 70 C., advantageously at 80 to 100 0., preferably a ratio of 1:1 to 2:1 being maintained.
  • superatmosphere pressure water having a temperature of more than 100 C. may also be used, e.g. 130 C.
  • the treatment with superheated steam is preferably carried out in columns, for example in sieve plate columns or baffle plate columns, to which the solution to be treated is supplied at the top and into which the superheated steam is injected at the bottom.
  • columns for example in sieve plate columns or baffle plate columns, to which the solution to be treated is supplied at the top and into which the superheated steam is injected at the bottom.
  • ten theoretical trays are adequate and often less than ten theoretical trays are suflicient.
  • Monocarboxylic acids are as a rule added as aqueous solutions whose concentration is measured so that the ratio of 1,4,5,6,7,7-hexachlorobicyclo-[2,2,1]-5-heptene-2,3-dicarboxylic acid to solvent is in the weight range from 0.8:1 to 1:0.8, preferably 1:1, and the concentration of the monocarboxylic acid in the aqueous phase is mainly 5 to 20% by weight.
  • Separation of the 1,4,5,6,7,7-hexachlorobicyclo-[2,2,1]- 5-heptene-2,3-dicarboxylic acid after the solution has been cooled preferably to to 60 C. may be carried out by methods conventionally used for separating crystals from mother liquor, for example by means of centrifuges or filters.
  • heptene- 2,3-dicarboxylic acid obtained by the process contains 1 mole of water of crystallization in addition to any adherent water.
  • This product may be used direct for the production of high grade colorless self-extinguishing polyesters.
  • EXAMPLE 1 Referring to the drawing, 379 parts per hour of liquid maleic anhydride at 70 C. is passed through line 2 and 955 parts per hour of 97.5% hexachlorocyclopentadiene which has been heated to 155 C. is passed through line 3 into a reaction tube 1 having a capacity of 3.4 parts by volume, whose diameter/height ratio is 1:58, which is arranged vertically and which has a jacket for cooling liquid to carry away heat.
  • the molar ratio of maleic anhydride to hexachlorocyclopentadiene is 1.1:1.
  • a temperature of about 140 C. is set up in the mixture. The temperature rises to about 175 C. by the exothermic reaction. It is kept at about 160 C. by cooling.
  • the melt thus obtained flows in an amount of 1334 parts per hour from the lower end of the reaction tube 1 through line 4 into a receiver 5 fitted with a stirrer and condenser. 570 parts of hot water at a temperature of to C. is supplied per hour to the receiver 5 through line 6.
  • the aqueous solution of 1,4,5,6,7,7 hexachlorobicyclo [2,2,1] 5 heptene 2, S-dicarboxylic acid formed is supplied to the top of a sieve tray column 7 having ten sieve trays.
  • the solution is passed into one of two crystallizing vessels 11 (used alternately) in which it is cooled to 15 C. with a residence time of about five hours.
  • 14,640 parts of crystal slurry is sucked off by a pump 12 and supplied to a centrifuge 13.
  • the crystal slurry is washed in the centrifuge with 2700 parts of 15% acetic acid solution supplied through line 14 and 12,600 parts 'of water supplied through line 15.
  • About 1300 parts of 1,4,5,6,7,7 hexachlorobicyclo [2,2,1] 5 heptene 2, 3-dicarboxylic acid per hour is obtained which contains 4.3% of water of crystallization and to which about 3.7%
  • EXAMPLE 2 An apparatus is used which is similar to that in Example 1 but a cascade of three vessels each provided with a stirrer and a jacket for cooling or heating fluid and whose capacity is from 0.9 to 1.2 parts by volume is provided instead of the reaction tube 1. 406 parts per hour of liquid maleic acid is supplied through line 2 at 70 C. and 982 parts per hour of 97.5% hexachlorocyclopentadiene at room temperature is supplied through line 3 to the series of vessels.
  • the molar ratio of maleic anhydride to hexachlorocyclopentadiene is 1.15:1.
  • the volume of the vessels and their cooling and heating means are so dimensioned that the reaction mixture has a mean residence time of sixtyfive minutes at 165 C. in the first vessel, fifty-eight minutes at 165 C. in the second vessel and seventy-seven minutes at 170 C. in the third vessel of the series.
  • the melt flows from this third vessel in an amount of 1388 parts per hour through line 4 into the receiver 5 provided with stirrer and condenser. 600 parts per hour of water at 80 to 90 C. is supplied through line 6 to the receiver 5.
  • the aqueous solution thus formed is supplied to the top of a baffie plate column 7 having ten trays.
  • the hourly supply of 1988 parts of the said solution meets a counter-current stream of 9940 parts per hour of steam which is supplied through line 8 at a temperature of 140 C.
  • the space-time yield is 9.68 kg. per liter of reaction volume per day.
  • a process for the production of pure 1,4,5,6,7,7- hexachlorobicyclo-[2,2,1]-5-heptene-2,3-dicarboxylic acid from hexachlorocyclopentadiene and maleic anhydride by heating wherein the reactants are supplied together and continuously to a reactor kept at a temperature of 120 to 200 C., are passed through the same with a mean residence time of two to seven hours, the efiluent reaction product is allowed to flow into water at a temperature of at least C., the solution thus obtained is treated by injection of superheated steam to remove chlorohydrocarbons, a lower saturated fatty acid or a lower saturated chlorinated fatty acid, is added to the solution which is then cooled and the crystalline 1,4,5, 6,7,7 hexachlorobicyclo [2,2,1] 5 heptene 2,3 dicarboxylic acid is separated.
  • a process for the production of 1,4,5,6,7,7-hexachlorobicyclo [2,2,1] 5 heptene-2,3-dicarboxylic acid from hexachlorocyclopentadiene and maleic anhydride wherein hexachlorocyclopentadiene and maleic anhydride are supplied together and continuously in a molar ratio of 08:13 to 1.3108 to a reactor kept at a temperature of from to 200 C., are passed through the same with a mean residence time of two to seven hours, the eflluent reaction product is allowed to flow into water having a temperature of from 70 to C., the solution thus obtained is treated by steam superheated up to 200 C.
  • a lower saturated fatty acid or a lower saturated chlorinated fatty acid is added to the solution in an amount of 0.05 to 1 times the weight of the 1,4,5,6,7,7-hexachlorobicyclo- [2,2,1]-5-heptene-2,3-dicarboxylic acid, which solution is then cooled and the 1,4,5,6,7,7-hexachlorobicyclo-[2,2,1]- 5-heptene-2,3dicarboxylic acid is separated.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US549352A 1965-05-14 1966-05-11 Continuous production of 1,4,5,6,7,7-hexachlorobicyclo - (2,2,1) - 5 - heptene - 2,3-dicarboxylic acid Expired - Lifetime US3449412A (en)

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US (1) US3449412A (enrdf_load_stackoverflow)
BE (1) BE681047A (enrdf_load_stackoverflow)
DE (1) DE1518552A1 (enrdf_load_stackoverflow)
GB (1) GB1139311A (enrdf_load_stackoverflow)
NL (1) NL6606233A (enrdf_load_stackoverflow)

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US5861528A (en) * 1996-01-22 1999-01-19 Mitsui Chemicals, Inc. Process for preparing diels-alder addition product from conjugated diolefin and acrylonitrile

Citations (2)

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Publication number Priority date Publication date Assignee Title
US2779769A (en) * 1952-09-10 1957-01-29 Hooker Electrochemical Co Poly-halogen-containing dicarboxylic acids and anhydrides
CA634620A (en) * 1962-01-16 B. Soloway Samuel Polyhalogeno bicyclic acids

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA634620A (en) * 1962-01-16 B. Soloway Samuel Polyhalogeno bicyclic acids
US2779769A (en) * 1952-09-10 1957-01-29 Hooker Electrochemical Co Poly-halogen-containing dicarboxylic acids and anhydrides

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DE1518552A1 (de) 1969-07-03
NL6606233A (enrdf_load_stackoverflow) 1966-11-15
BE681047A (enrdf_load_stackoverflow) 1966-10-17
GB1139311A (en) 1969-01-08

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