US3896011A - Process for the preparation of sebacic acid - Google Patents

Process for the preparation of sebacic acid Download PDF

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US3896011A
US3896011A US436275A US43627574A US3896011A US 3896011 A US3896011 A US 3896011A US 436275 A US436275 A US 436275A US 43627574 A US43627574 A US 43627574A US 3896011 A US3896011 A US 3896011A
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dimethyl sebacate
solution
electrolytic
weight
electrolytic solution
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Toshiro Isoya
Rinichi Kakuta
Chikayuki Kawamura
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Chemical Industry Co Ltd
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Priority claimed from JP48034863A external-priority patent/JPS49117418A/ja
Priority claimed from JP11121873A external-priority patent/JPS563434B2/ja
Priority claimed from JP48141604A external-priority patent/JPS5089317A/ja
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/29—Coupling reactions

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  • ABSTRACT A process for preparing sebacic acid of high purity in a high yield from adipic acid by conducting the elec trolytic condensation of monomethyl adipate at a high current efficiency and a low electric cell voltage. This process is characterized in that electrolytic condensa- Mar. 26, 1973 Japan c i r r.
  • This invention relates to a process for preparing sebacic acid from adipic acid, and more particularly to a process for electrolytically preparing sebacic acid from monomethyl adipate and an alkali salt thereof.
  • the reaction of electrochemically condensing carboxylic acids is generally called the Kolbe reaction
  • a B (mole '36) is defined as degree a of neutralization" of the abovementioned methanol solution.
  • Provision of an electrolytic call of an appropriate size is required for practicing the process on an industrial scale by employing the above-mentioned electrolytic solution while the inside pressure of the cell is determined by the volume and structure thereof.
  • an electrolytic cell comprising parallelly disposed cathode and anode plates between which an electrolytic solution is passed, which is usually employed in organic electrolytic reactions
  • the process is conducted on an industrial scale, it is desired that the flow passage of the electrolytic solution is within a range of from 50 to 200 em, but if the flow passage of the electrolytic solution is longer, the inside pressure of the cell becomes higher and there is caused such a dis advantage that the current efficiency is lowered.
  • distillation As known means for separating from the resulting electrolytic solution dimethyl sebacate formed by the above electrolytic reaction, there can be mentioned distillation, crystallization and extraction.
  • the distillation method is defective in that azeotropy is caused between dimethyl sebacate and monomethyl adipate and they cannot be separated from each other.
  • the crystallization method there are such disadvantages that the operation should be conducted at a low temperature and occlusion of monomethyl adipate in the resulting crystals cannot be avoided.
  • the extraction method if water is employed as an extraction solvent, it is necessary to employ it in a very large amount, and in general, water should be used in an amount of at least 3 parts per part of the residual liquid left after removal of methanol from the electrolytic solution.
  • Hydrolysis of dimethyl sebacate with a mineral acid for formation of sebacic acid is accomplished according to the conventional technique by adding water in an amount of at least 4 parts by weight per part by weight of the dimethyl sebacate layer prior to the acid hydrolysis, in order to prevent the formed methanol and sebacic acid from undergoing reaction under the action of the hydrolysis agent, and carrying out the hydrolysis reaction at a temperature higher than 100C. under an elevated pressure.
  • water in an amount of at least 4 parts by weight per part by weight of the dimethyl sebacate layer prior to the acid hydrolysis, in order to prevent the formed methanol and sebacic acid from undergoing reaction under the action of the hydrolysis agent, and carrying out the hydrolysis reaction at a temperature higher than 100C. under an elevated pressure.
  • such hydrolysis process involves complicated steps. resulting in great disadvantages when the process is carried out on an industrial scale.
  • FIG. 1 is a curve illustrating the relation between the inside pressure of the electrolytic cell and the electric current efficiency
  • FIG. 2 is a curve illustrating the relation of the liquid velocity in the electrolytic cell to the electric current efficiency, the inside pressure of the electrolytic cell and the electrolytic cell voltage;
  • FIG. 3 is a flow sheet showing an embodiment of this invention, in which reference numerals l, 2 and 4 indicate an electrolytic solution tank, an electrolytic cell and an extraction column. respectively.
  • Monomethyl adipate which is used as the starting material in the process of this invention, is prepared from adipic acid and methanol. in this esterification reaction, it is preferred that water is present in the reaction mixture in an amount of at least 1 mole per mole of adipic acid present in the reaction mixture.
  • Various electrolytic solutions were prepared by neutralizing a methanol solution of monomethyl adipate and dimethyl sebacate with sodium hydroxide so that the concentration of monomethyl adipate was 20% by weight and the neutralization degree a was 30 mole and by changing the concentration of dimethyl sebacate as shown in Table 1 given below.
  • Either a cathode plate or an anode plate had a current-applied area of 2 X 50 cm.
  • the cathode was composed of a SUS 27 plate having a thickness of 2 mm and the anode was composed of a titanium plate of a thickness of 2 mm plated with platinum in a thickness of 2 microns.
  • An electrolytic cell used had inlet and outlet openings for the electrolytic solution, and the electrolytic solution was passed through both the electrodes at a liquid velocity of 2 m/sec at a current density of 20 A/dm. The temperature of the electrolytic solution at the cell outlet was maintained at 55C.
  • the electrolysis' was conducted for l0 hours under theiforegoing conditions while removing a part ofthe'electrolytic solution and supplying methanol.
  • neutralizing base examples include hydroxides, carbonates, methylates and ethylates of lithium, sodium and potassium, ammonia, dimethylamine, trimethylamine, ethylamine, ethanolamine and the like.
  • Methanol is most preferred as a reaction solvent, but ethanol, isopropanol, ethylene glycol, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, acetonitrile, propionitrile, tetrahydrofuran and water can be used singly or as one component of a mixed solvent.
  • Provision of an electrolytic cell of a certain size is required for conducting the electrolysis on an industrial scale with use of the above-mentioned electrolytic solution, and the inside pressure of the electrolytic cell used is determined by the volume and structure of the cell.
  • an electrolytic cell customarily used for the organic electrolysis reaction cathode and anode plates are disposed in parallel to each other and an electrolytic solution is passed between the two electrodes.
  • the flow passage of the electrolytic solution is within a range of from 50 to 200 cm.
  • the inside pressure of the electric cell is increased and hence, there is caused an undesired reduction of the electric current efficiency.
  • the relationship between the inside pressure of the electric cell and the electric current efficiency is known in the art. For reference, results of experiments made with a view to demonstrating this relationship are described below.
  • any of the electrolytic cells customarily used for organic electrolytic reactions can be used as far as it has such a structure that the electrolytic solution can pass between the electrodes at such a high flow rate as mentioned above.
  • an electrolytic cell comprising parallelly disposed cathode and anode plates and a polyethylene plate disposed between the electrodes to define the electrode distance, in which a hole is perforated at the central portion of the polyethylene plate so that the electrolytic solution can pass therethrough.
  • the current-applied area is determined by the size of this hole and the electrode distance is defined by the thickness of the polyethylene plate.
  • the electrolytic solution is fed from an inlet opening, and a part of the electrolytic solution is reacted while it passes through the space between the electrodes. Then, the electrolytic solution is withdrawn from an outlet opening and recycled to an electrolytic solution tank.
  • anode As a material for the anode, there are employed, for example, platinum, ruthenium, rhodium, palladium, gold and alloys thereof. In general, these metals are used in the form as plated on a substrate such as titanium, tantalum and iron.
  • a material for the cathode a substance having a low hydrogen overvoltage is preferably used but the material for the cathode is not particularly critical in this invention. Platinum, iron, nickel, stainless steel and the like may preferably be employed.
  • the distance between the cathode and the anode is within a range of from I to 3 mm. in general, it is appropriate that the length of the flow passage of the electrolytic solution is within a range of from 50 to 200 cm. It is desired that the temperature of the electrolytic solution is higher than 40C., but it should be lower than the boiling point of the electrolytic solution.
  • the current density is not particularly critical in this invention but it is generally preferred that the electrolysis is carried out at a current density of 20 to 40 A/dm Dimethyl sebacate thus prepared should be separated from the electrolytic solution. This separation will now be illustrated by reference to the flow sheet of FIG. 3.
  • numeral 1 represents an electrolytic solution tank. and the electrolytic solution is circulated to an electrolytic cell 2.
  • the electrolytic solution is a methanol solution containing monomethyl adipate, dimethyl sebacate and minor amounts of such by-products as dimethyl adipate, methyl n-valerate, methyl w-hydroxyvalerate and methyl allylacetate.
  • a part of the electrolytic solution is withdrawn and methanol is removed at a distillation column 3 while the remainder is forwarded to an extraction column 4.
  • the withdrawn electrolytic solution may be forwarded to the extraction column 4 without removal of methanol.
  • An organic solvent is fed from a feed inlet 5 and for warded to the lower portion of the extraction column 4 together with the electrolytic solution.
  • the feed inlet 5 for an organic solvent may be provided at a position other than the point shown in FIG.
  • the organic solvent layer containing dimethyl sebacate overflowing from the head of the extraction column 4 is fed to a distillation column 7 where the organic solvent fed from the feed inlet 5 is distilled and is used again for extraction.
  • a liquor composed mainly of dimethyl sebacate is recovered from the bottom portion of the column 7, and according to need, it is forwarded to another distillation column (not shown) to obtain a higher purity product of dimethyl sebacate.
  • An aqueous solution containing monomethyl adipate and its alkali salt is withdrawn from the bottom portion of the extraction column 4 and is fed to a distillation column 8, where water is distilled from the column head and is used again for extraction.
  • Monomethyl adipate and its alkali salt are withdrawn from the bottom portion of the column 8, and are circulated to the electrolytic solution tank and used for the electrolysis reaction.
  • Water and organic solvent are used for the extraction in such amounts as sufficient to form an organic layer and an aqueous layer. In general, water is used in an amount of 0.2 to 2 parts by weight per part by weight of the electrolytic solution to be extracted and the organic solvent is used in an amount of 0.2 to 2 parts by weight per part by weight of the electrolytic solution.
  • the electrolytic solution to be extracted was a methanol solution containing 30% by weight of dimethyl sebacate, 20% by weight of monomethyl adipate, 9% by weight of sodium monomethyl adipate and minor amounts of such by-products as dimethyl adipate, methyl nwalerate, methyl w-hydroxyvalerate and methyl allylacetate, and methanol was removed from this electrolytic solution by distillation. Then, 500 g. of water was added to lOO g. of the residual liquid and the mixture was agitated at room temperature to form two layers. The upper oil layer contained mainly dimethyl sebacate and monomethyl adipate and the lower aqueous layer contained mainly monomethyl adipate and its sodium salt.
  • the foregoing defect involved in the extraction step can be effectively overcome. More specifically, as is seen from the results obtained by adding water and n-heptane to g of the residual liquid left after removal of methanol, and agitating the mixture at room temperature to separate it into two layers, which are also shown in Table 4, the upper n-heptane layer comprises dimethyl sebacate alone and the lower aqueous layer comprises predominantly monomethyl adipate and its sodium salt.
  • the dimethyl sebacate so separated is hydrolyzed with use of a mineral acid to obtain sebacic acid.
  • a mineral acid to obtain sebacic acid.
  • the hydrolysis can be greatly accelerated and advanced very promptly.
  • unreacted dimethyl sebacate and monomethyl sebacate are incorporated into precipitated crystals of sebacic acid, and it takes a long time to complete the hydrolysis reaction.
  • the hydrolysis reaction can be accomplished promptly without incorporation of unreacted dimethyl sebacate or monomethyl sebacate into sebacic acid.
  • the hydrolysis is carried out by removing methanol formed by the reaction from the reaction system, the hydrolysis reaction can be accelerated, and modification of methanol with the mineral acid can be effectively prevented.
  • the removal of methanol may be effected by, for example, distillation. It is preferred that the methanol concentration in the liquor to be hydrolyzed is low, and in general it is maintained below 0. l% by weight.
  • Nitric acid is preferred as the mineral acid, but sulfuric acid, hydrochloric acid and the like can also be employed. It is preferred that the acid concentration is within a range of from l to 30% by weight.
  • the hydrolysis is conducted at a temperature of at least 90C., preferably at least 100C. Generally, the hydrolysis is conducted at a temperature of 100 120C.
  • dimethyl sebacate is formed by the electrolytic condensation of monomethyl adipate and its sodium salt in a methanol solution and when water and an organic solvent capable of dissolving dimethyl sebacate and insoluble in water are added to the resulting electrolytic solution or such organic solvent alone is added to the resulting electrolytic solution to form two layers and water is added to the organic solvent layer, thereby to separate the electrolytic solution into aqueous and organic solvent layers and extract dimethyl sebacate into the organic solvent layer, it is possible to separate and recover dimethyl sebacate of very high purity.
  • Both the electrodes of the cell had a current-applied area of2 X 50 cm.
  • the cathode was composed of a SUS 27 plate having a thickness of 2 mm and the anode was composed of titanium plate of a thickness of 2 mm plated with platinum in a thickness of 2 u.
  • a polyethylene plate of a thickness of 2 mm perforated so that the current-applied area was 2 X 50 cm was disposed between both the electrodes to define the electrode distance as 2 mm.
  • the electrolytic cell had inlet and outlet openings for the electrolytic solution and the electrolytic solution was passed between both the electrodes at a liquid velocity of 2 m/sec. The electrolysis was carried out at a current density of 20 A/dm and an electrolytic solution temperature of C. for 10 hours.
  • EXAMPLE 2 The Kolbe synthesis reaction was carried out under the same conditions as adopted in Example 1 by using sodium hydroxide as the neutralization base, adjusting the neutralization degree a to 30 mole and changing the current density as indicated in Table 6, Results are shown in Table 6.
  • a cathode was composed of a titanium plate of a thickness of 2 mm and an anode was composed of a titanium plate of a thickness of 2 mm plated with platinum in a thickness of 3 t. Both the electrodes had a current-applied area of 1 X 150 cm, and a polyester plate perforated so that it had the above current applied area was disposed to define the electrode distance as 3 mm.
  • the electrolytic cell had inlet and outlet LII openings for -the.e1ectrolytic solution and the electro lytic solution was flown between the electrodes at a liquid velocity of 3 rnm/sec.
  • the electrolysis was conducted at a current density of 25 A/dm and an electrolytic solution temperature of 60C. at the outlet of the cell.
  • the average inside pressure of the electrolytic cell was 1.31 atm. and the electrolytic cell voltage was 1 volts.
  • the amount of formed dimethyl sebacate was determined by gas chromatography from which it was found that the electric current efficiency was 83%.
  • EXAMPLE 5 With use of 5 Kg of an electrolytic solution containing 40% by weight of monomethyl adipate, which was neutralized with sodium hydroxide so that the neutralization degree a was 10 mole and 20% by weight of dimethyl sebacate, the balance being methanol. the electrolysis was carried out for 2 hours under the same conditions as adopted in Example 4 except that the liquid velocity of the electrolytic solution. the length of the electrolytic solution flow passage and the electrode distance were changed to 4 m/sec. cm and 2 mm, respectively. The inside pressure of the electrolytic cell was 1.48 atm. and the electrolytic cell voltage was 17 volts.
  • the amount of dimethyl sebacate formed was determined by gas chromatography, from which it was seen that the electric current efficiency was 88%.
  • EXAMPLE 6 With use of 5 Kg of an electrolytic solution containing 10% by weightof monomethyl adipate, which was neutralized with sodium hydroxide so that the neutralization degree a was 50 mole and 30% by weight of dimethyl sebacate, the balance being methanol, the electrolysis was carried out under the same conditions as adopted in Example 5 except that the liquid velocity of the electrolytic solution in the cell was changed to 2.5 m/sec. The inside pressure of the electrolytic cell was 1.25 atm. and the electrolytic cell voltage was 14 volts.
  • the amount of dimethyl sebacate formed was determined by gas chromatography, from which it was found that the current efficiency was 81%.
  • EXAMPLE 7 An electrolytic solution containing 15.5% by weight of monomethyl adipate, 7.3% by weight of potassium monomethyl adipate, 22.1% by weight of dimethyl sebacate and 2.5% by weight of other by-products, the balance being methanol, was withdrawn from an electrolytic cell without removal of methanol from the electrolytic solution. Then, 100 g of water and 100 g of cyclohexane, n-hexane, n-heptane or isooctane were added to 200 g of the so withdrawn electrolytic solution, and the mixture was agitated at 40C. to separate it into two layers.
  • EXAMPLE 8 The extraction operation was conducted by employing. a counter-current extraction column having an inner diameter of 35 mm and a column length of 1200 mm. An electrolytic solution containing 12.7% by weight of monomethyl adipate, 5.2% by weight of potassium monomethyl adipate, 19.5% by weight of dimethyl sebacate and 2.4% of other by-products, the balance being methanol, extracted. A mixture of 1 part by weight of the above electrolytic solution and a part by weight of cyelohexane was fed under agitation at a rate of 5 m/hr from the bottom portion of the extraction column, and water was fed at a rate of 1 m/sec from the head portion of the extraction column, thereby to effect the counter-current extraction at room temperature.
  • the concentration of dimethyl sebacate in the cyclohexane layer flowing from the upper portion of the column was 22.8% but the concentration of monomethyl adipate was lower than 0.01% by weight.
  • the concentration of dimethyl sebacate in the aqueous layer withdrawn from the lower portion of the column was 2.1% by weight but the concentration of monomethyl adipate was 8.9% by weight.
  • EXAMPLE 9 Methanol was removed by distillation from an electrolytic solution containing 20.4% by weight of dimethyl sebacate, 10.0% by weight of monomethyl adipate, 3.5% by weight of potassium monomethyl adipate and 3.5% by weight of other by-products, the balance being methanol. Then, 500 g of n-heptane was added to 500 g of the residual liquor, and the mixture was agitated at room temperature to separate it into two layers. The upper layer contained 25.8% by weight of dimethyl sebacate and 1.6% by weight of monomethyl adipate. Then, 100 g of water was added to 100 g of this n-heptane layer and the mixture was agitated to separate it into two layers.
  • the upper n-heptane layer contained 25.3% by weight of dimethyl sebacate and less than 0.01% by weight of monomethyl adipate, and the lower aqueous layer contained 1.9% by weight of monomethyl adipate and less than 0.01% by weight of dimethyl sebacate. From these results, it can readily be understood that dimethyl sebacate could be separated from monomethyl adipate quite effectively in this Example.
  • the lower layer obtained at the first extraction step was an oil layer containing 41.4% by weight of monomethyl adipate, 23.5% by weight of dimethyl sebacate, 19.6% by weight of n-heptane and potassium monoethyl adipate. After removal of n-heptane from the oil layer by distillation, the residual liquor was returned to the electrolytic solution tank and subjected to the electrolysis.
  • EXAMPLE 10 A 2 liter capacity glass vessel was charged with 100 g of dimethyl sebacate formed by the electrolysis and 1.5 Kg of an aqueous solution containing 18% by weight of nitric acid, and the resulting mixture was violently agitated and refluxed under atmospheric pressure. ln this manner, the hydrolysis was carried out for 3 hours while removing methanol formed by the hydrolysis reaction by distillation. At the time of termination of the reaction, the rate of hydrolysis was 99.9 mole The methanol concentration in the resulting liquor was maintained below 0.03% by weight and sebacic acid formed by the hydrolysis was dissolved in the reaction medium and was not precipitated.
  • EXAMPLE 1 1 With use of 100 g of dimethyl sebacate formed by the electrolysis and 1 Kg of an aqueous solution containing 24% by weight of nitric acid, the hydrolysis was carried out for 5 hours in the same manner as in Example 10. The obtained degree of hydrolysis was 97.2 mole the methanol concentration in the resulting liquor was maintained below 0.03% by weight and all the formed sebacic acid was dissolved in the reaction medium without any deposition.
  • EXAMPLE 12 With use of 100 g of dimethyl sebacate formed by the electrolysis and 1 Kg of an aqueous solution containing 18% by weight of nitric acid, the hydrolysis was carried out in the same manner as in Example 10. The obtained degree of hydrolysis was 94.8 mole The methanol concentration in the resulting liquid was 0.05% by weight and all the formed sebacic acid was dissolved in the reaction medium.
  • the so formed liquor was cooled to room temperature to precipitate crystals of sebacic acid, which were recovered by filtration, washed with 100 g of water and dissolved in 200 g of water at 130C. under a pressure of 2.7 Kg/cm to effect recrystallization.
  • the resulting crystals were recovered by filtration, washed with 100 g of water and then dried to obtain g of pure sebacic acid having a melting point of 134C.
  • EXAMPLE 13 A mixture comprising 1 mole of adipic acid, 5 moles of water, 5 moles of methanol and 0.2 mole of dimethyl adipate was reacted under atmospheric pressure for 5 hours to form monomethyl adipate. The reaction mixture was subjected to distillation and dimethyl adipate was separated.
  • Both the electrodes of an electrolytic cell used had a current-applied area of 2 X cm.
  • the cathode was composed of a SUS plate having a thickness of 2 mm and the anode was composed of a titanium plate of a thickness of 2 mm plated with platinum in a thickness of2 pt.
  • a polyethylene plate ofa thickness of 2 mm perforated so that it had a current-applied area of 2 X 100 cm was disposed between both the electrodes to define the electrode distance as 2 mm.
  • the electrolytic cell had inlet and outlet openings for the electrolytic solution, and the electrolytic solution was passed between both the electrodes at a liquid velocity of 3 m/sec.
  • the electrolysis was conducted at a current density of Aldm at an electrolytic solution temperature of 55C.
  • the dimethyl sebacate concentration was 21% by weight
  • the monomethyl adipate concentration was 18% by weight
  • the neutralization degree was 27 mole
  • 10 Kg of this withdrawn electrolytic solution was subjected to countercurrent extraction to separate dimethyl sebacate therefrom.
  • the dimethyl sebacate concentration was 23% by weight and the monomethyl adipate concentration was lower than 0.01% by weight.
  • the so recovered cyclohexane solution was subjected to fractional distillation to remove low-boiling-point components such as cyclohexane, methanol, water, methyl n-valerate, methyl w-hydroxyvalerate, methyl allylacetate and dimethyl adipate, and then, dimethyl sebacate was distilled and purified.
  • the amount of the so recovered dimethyl sebacate was 1.4 Kg, and the product had a purity higher than 99.9% and a melting point of 264C.
  • a process for preparing dimethyl sebacate comprising subjecting to an electrolytic condensation in an electrolytic cell a solution of monomethyl adipate and an alkali salt thereof in methanol, the improvement which comprises maintaining the concentration of dimethyl sebacate in the solution at a level of at least 5% by weight, and passing the solution through the cell at a liquid velocity of at least 2.5 m/sec.
  • a process for preparing dimethyl sebacate comprising subjecting to an electrolytic condensation a solution of monomethyl adipate and an alkali salt thereof in methanol, the improvement which comprises maintaining the concentration of dimethyl sebacate in the solution at a level of at least 5% by weight; passing the solution through the electrolytic cell at a liquid velocity of at least 2.5 mlsee; withdrawing the resulting electrolytic solution containing dimethyl sebacate and combining it with an organic solvent capable of dissolving dimethyl sebacate and insoluble in water and with water to separate the withdrawn electrolytic solution into an aqueous layer substantially free of dimethyl sebacate and an organic solvent layer containing the dimethyl sebacate.
  • organic solvent is a member selected from the group consisting of n-hexane, n-heptane, n-octane, isooctane and cyclohexane.
  • a process for preparing sebaeic acid comprising subjecting to an electrolytic condensation a solution of monomethyl adipate and an alkali salt thereof in methanol to produce dimethyl sebacate and thereafter hydrolyzing the dimethyl sebacate to sebacic acid, the improvement which comprises maintaining the concentration of dimethyl sebacate in the solution at a level of at least 5% by weight; passing the solution through the electrolytic cell at a liquid velocity of at least 2.5 m/sec.; withdrawing the resulting electrolytic solution containing dimethyl sebacate and combining it with an organic solvent capable of dissolving dimethyl sebacate and insoluble in water and with water to separate the withdrawn electrolytic solution into an aqueous layer and an organic solvent layer whereby the dimethyl sebacate is extracted in the organic solvent layer; and hydrolyzing the separated dimethyl sebacate using an aqueous solution of a mineral acid in which dimethyl sebacate is present in an amount of at most the amount corresponding to the saturation solubility of sebacic acid in the aqueous

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JP1188373A JPS5323816B2 (xx) 1973-01-31 1973-01-31
JP48034863A JPS49117418A (xx) 1973-03-26 1973-03-26
JP11121873A JPS563434B2 (xx) 1973-10-03 1973-10-03
JP48141604A JPS5089317A (xx) 1973-12-17 1973-12-17

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Cited By (12)

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US4124453A (en) * 1975-09-29 1978-11-07 National Research Development Corporation Electrochemical processes
DE2830144A1 (de) * 1977-07-20 1979-01-25 Asahi Chemical Ind Elektrolytisches verfahren zur herstellung von sebacinsaeure aus adipinsaeure
US4237317A (en) * 1977-07-20 1980-12-02 Asahi Kasei Kogyo Kabushiki Kaisha Process for producing sebacic acid
US4525251A (en) * 1981-05-28 1985-06-25 Asahi Kasei Kogyo Kabushiki Kaisha Process for producing dimethyl esters of higher dibasic acid
US5290404A (en) * 1990-10-31 1994-03-01 Reilly Industries, Inc. Electro-synthesis of alcohols and carboxylic acids from corresponding metal salts
US20130186770A1 (en) * 2009-07-23 2013-07-25 Ceramatec, Inc. Device and method of obtaining diols and other chemicals using decarboxylation
US9677182B2 (en) 2011-01-25 2017-06-13 Ceramatec, Inc. Production of fuel from chemicals derived from biomass
US9752081B2 (en) 2009-07-23 2017-09-05 Ceramatec, Inc. Method of producing coupled radical products from biomass
US10145019B2 (en) 2010-07-21 2018-12-04 Enlighten Innovations Inc. Custom ionic liquid electrolytes for electrolytic decarboxylation
EP3438271A3 (en) * 2017-08-02 2019-06-19 Cathay R&D Center Co., Ltd. Decanedioic acid produced by microbial fermentation and preparation method thereof
CN111850596A (zh) * 2020-07-13 2020-10-30 万华化学集团股份有限公司 一种电化学合成癸二酸酯类化合物的连续生产方法
CN113416969A (zh) * 2021-06-18 2021-09-21 万华化学集团股份有限公司 一种癸二酸二甲酯电化学合成方法

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US2439425A (en) * 1946-04-01 1948-04-13 Du Pont Process for preparing dialkyl esters of dicarboxylic acids
US3589990A (en) * 1968-02-29 1971-06-29 Vnii Pi Monomerov Process for the production of sebacic acid
US3756928A (en) * 1970-08-12 1973-09-04 Basf Ag Ls process for the manufacture of sebacic acid diesters of higher alcoho
US3787299A (en) * 1970-03-28 1974-01-22 Basf Ag Electrolytic condensation of carboxylic acids

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Publication number Priority date Publication date Assignee Title
US2439425A (en) * 1946-04-01 1948-04-13 Du Pont Process for preparing dialkyl esters of dicarboxylic acids
US3589990A (en) * 1968-02-29 1971-06-29 Vnii Pi Monomerov Process for the production of sebacic acid
US3787299A (en) * 1970-03-28 1974-01-22 Basf Ag Electrolytic condensation of carboxylic acids
US3756928A (en) * 1970-08-12 1973-09-04 Basf Ag Ls process for the manufacture of sebacic acid diesters of higher alcoho

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4124453A (en) * 1975-09-29 1978-11-07 National Research Development Corporation Electrochemical processes
DE2830144A1 (de) * 1977-07-20 1979-01-25 Asahi Chemical Ind Elektrolytisches verfahren zur herstellung von sebacinsaeure aus adipinsaeure
FR2398034A1 (xx) * 1977-07-20 1979-02-16 Asahi Chemical Ind
US4237317A (en) * 1977-07-20 1980-12-02 Asahi Kasei Kogyo Kabushiki Kaisha Process for producing sebacic acid
US4525251A (en) * 1981-05-28 1985-06-25 Asahi Kasei Kogyo Kabushiki Kaisha Process for producing dimethyl esters of higher dibasic acid
US5290404A (en) * 1990-10-31 1994-03-01 Reilly Industries, Inc. Electro-synthesis of alcohols and carboxylic acids from corresponding metal salts
US9752081B2 (en) 2009-07-23 2017-09-05 Ceramatec, Inc. Method of producing coupled radical products from biomass
US20130186770A1 (en) * 2009-07-23 2013-07-25 Ceramatec, Inc. Device and method of obtaining diols and other chemicals using decarboxylation
US9957622B2 (en) * 2009-07-23 2018-05-01 Field Upgrading Limited Device and method of obtaining diols and other chemicals using decarboxylation
US10968525B2 (en) 2009-07-23 2021-04-06 Enlighten Innovations Inc. Device and method of obtaining diols and other chemicals using decarboxylation
US10145019B2 (en) 2010-07-21 2018-12-04 Enlighten Innovations Inc. Custom ionic liquid electrolytes for electrolytic decarboxylation
US9677182B2 (en) 2011-01-25 2017-06-13 Ceramatec, Inc. Production of fuel from chemicals derived from biomass
EP3438271A3 (en) * 2017-08-02 2019-06-19 Cathay R&D Center Co., Ltd. Decanedioic acid produced by microbial fermentation and preparation method thereof
US10851394B2 (en) 2017-08-02 2020-12-01 Cathay Biotech Inc. Decanedioic acid produced by microbial fermentation process and preparation method thereof
US11802298B2 (en) 2017-08-02 2023-10-31 Cathay Biotech Inc. Decanedioic acid produced by microbial fermentation process and preparation method thereof
CN111850596A (zh) * 2020-07-13 2020-10-30 万华化学集团股份有限公司 一种电化学合成癸二酸酯类化合物的连续生产方法
CN111850596B (zh) * 2020-07-13 2021-04-20 万华化学(四川)有限公司 一种电化学合成癸二酸酯类化合物的连续生产方法
CN113416969A (zh) * 2021-06-18 2021-09-21 万华化学集团股份有限公司 一种癸二酸二甲酯电化学合成方法

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DE2404560A1 (de) 1974-08-01
DE2404560B2 (de) 1981-07-23
CA1057232A (en) 1979-06-26
GB1425669A (en) 1976-02-18
CH598176A5 (xx) 1978-04-28
FR2216261A1 (xx) 1974-08-30
FR2216261B1 (xx) 1978-07-13
DE2404560C3 (de) 1982-04-29

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