US3616319A - Electrolytic hydrodimerization of olefinic compounds - Google Patents

Electrolytic hydrodimerization of olefinic compounds Download PDF

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Publication number
US3616319A
US3616319A US704279A US3616319DA US3616319A US 3616319 A US3616319 A US 3616319A US 704279 A US704279 A US 704279A US 3616319D A US3616319D A US 3616319DA US 3616319 A US3616319 A US 3616319A
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membrane
catholyte
anolyte
olefinic
membranes
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US704279A
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Robert Johnson
Roy E Jones
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Monsanto Co
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Monsanto Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2275—Heterogeneous membranes
    • 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
    • C25B3/295—Coupling reactions hydrodimerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene

Definitions

  • an aqueous solution containing at least one of the nitriles, esters and/or carboxamides and an electrolytic salt e.g., a quaternary ammonium or amine salt
  • an electrolytic salt e.g., a quaternary ammonium or amine salt
  • a strong acid usually a mineral acid such as sulfuric acid
  • hydrogen ions from the anolyte permeate through the membrane into the cathode compartment and, in an electrolytic reaction utilizing such hydrogen ions, the nitriles, esters and/r carboxamides are dimerized at the cathode.
  • a variety of membrane-reinforcing materials have been tested in attempts to improve the length and consistency of membrane service life and thereby reduce contamination of the anolyte and catholyte without an intolerable sacrifice of process efficiency.
  • membranes containing a nonwoven fabric embedded within a polymeric matrix have been tried without significant success.
  • the use of a plurality of thin unreinforced membranes has also failed to adequately improve the length and reproducibility of membrane service life.
  • a commercially acceptable type of reinforced membrane is very desirable, and it is an object of this invention to provide an electrohydrodimerization process utilizing such a reinforced membrane.
  • the present invention provides a process for producing hydrodimers of olefinic compounds which comprises passing electric current through an aqueous olefinic nitrile-, esteror carboxamide-containing catholyte separated from an aqueous acidic anolyte by an ion-exchange membrance comprising a solid electrically conductive polymeric cation-permeable matrix reinforced by at least two substantially parallel sheets of woven glass fabric embedded within said matrix.
  • FIG. I is a perspective view of a rectangular piece of an ion-exchange membrane having a polymeric matrix partly broken away to show a plurality of layers of glass fabric embedded therein
  • FIG. 11 is a schematic vertical section view of an electrolytic cell assembly in which the process of this invention can be carried out with a membrane of the type shown in FIG. I, and FIG.
  • III is a graph in which the durability of the membranes used in the process of this invention is compared with that of other membranes heretofore suggested for similar use by plotting the water leakage rate of each membrane as a function of the length of time it has been in use in the electrohydrodimerization process.
  • membrane 3 which is composed of a solid polymeric ion-exchange material having a substantially uniform thickness is partially broken away to show an upper layer 4 and a lower layer 5 of woven glass fabric.
  • the polymeric material can be of any composition that permits a suitable rate of permeation of cations (e.g., hydrogen ions) from the anolyte to the catholyte of the electrohydrodimerization cell described herein.
  • cations e.g., hydrogen ions
  • a composition preferred for use as the membrane matrix in the present invention may be prepared by polymerizing a mixture of compounds containing at least about 20 mol percent and preferably between about 30 and about mol percent of one or more polyvinyl aromatic compounds e.g., divinyl benzenes, divinyl naphthalenes, divinyl diphenyls, alkyI-substituted derivatives thereof, etc.) and less than 80 mol percent of other monovinyl compounds which copolymerize with the polyvinyl aromatic compounds (e.g., styrene, vinyl naphthalenes, alkylsubstituted derivatives thereof, etc.) while maintaining the mixture in a suitable inert solvent (e.g., an aromatic hydrocarbon such as diethylbenzene) under conditions preferably preventative of evaporation of the solvent.
  • a suitable inert solvent e.g., an aromatic hydrocarbon such as diethylbenzene
  • Polymerization can be effected with any of the well-known expedients such as pressure, heat (e.g., 50l00 C.) and/or a catalytic accelerator such as benzoyl peroxide, and is continued until an insoluble, infusible gel is formed substantially throughout the solution.
  • the resulting gel structure is then sulfonated in a solvated condition and preferably to such an extent that there are not more than about four equivalents of sulfonic acid groups formed for each mol of polyvinyl aromatic compound in the polymer and not less than about one equivalent of sulfonic acid groups formed for each [0 mols of vinyl aromatic compound in the polymer.
  • Sheets 4 and 5 have the visibly open structures (preferably but not necessarily 50-75 percent of total fabric area) that are characteristic of woven fabrics and are woven from glass fibers which are preferably staple fibers but which may be alternatively prepared from continuous filaments.
  • Fabric weave and weight may be varied widely, although a 2] X 14 fiber weave and a weight of 5-15 ounces per square yard are exemplary.
  • the choice of a particular glass fabric depends on the desired properties of the membrane. Fiber orientation in the sheets can be parallel or biased and, if desired for greater rigidity, the filaments of adjacent sheets can be entangled by a needling or stitching operation before polymerization of the matrix.
  • 9-ounce 21 X 14 thread count woven glass cloth is treated with a sizing compound (e.g., the mixture of methacrylic acid and chromium chloride known in the art as Volan) for greater polymer-glass adhesion and then cut into sheets having dimensions suitable for the intended use (e.g., 36 inches X40 inches for an electrohydrodimerization cell of preferred size).
  • a sizing compound e.g., the mixture of methacrylic acid and chromium chloride known in the art as Volan
  • At least two of the sheets of sized glass cloth are horizontally stacked on a glass plate in a polymerization vessel having horizontal dimensions slightly larger than those of the sheets after which filaments of adjacent sheets may be entangled by needling or stitching.
  • a second glass plate is then laid on the sheets of glass fabric and the stack of glass plates and sheets of glass fabric are covered with a mixture containing approximately equal amounts of. polymerizable compounds and solvent plus a catalytically effective amount of a polymerization catalyst of the type described hereinbefore.
  • the mixture is heated to a suitable polymerization temperature (preferably 80-90 C.) and then maintained at such a temperature for several hours after which the resulting solid unfractured gel-like matrix with the glass fabric sheets embedded there in is removed from between the glass plates.
  • Polymerization solvent can then be removed by washing although it is generally advantageous to replace it directly with a suitable sulfonation solvent (e.g., a hydrocarbon such as heptane) by leaching the polymerized gel in such a solvent.
  • a suitable sulfonation solvent e.g., a hydrocarbon such as heptane
  • the gel is rendered selectively cation-permeable by treatment with a suitable sulfonating agent such as sulfuric acid containing dissolved sulfur trioxide, e.g., at 5060 C., until sulfonation of the aromatic nuclei in the gel has taken place to the extent described hereinbefore.
  • a suitable sulfonating agent such as sulfuric acid containing dissolved sulfur trioxide, e.g., at 5060 C.
  • the sulfonating agent and solvent are then washed out of the gel, preferably by immersion in water which prevents drying and possible cracking of the gel before cell installation. Removal of solvent from the gel leaves a microporous structure in which the proportion of pore space determines the water transfer properties of the membrane during cell use.
  • the resulting membrane When the polymerization step is carried out with a mixture containing a proportion of solvent within the aforedescribed range, the resulting membrane normally has a degree of porosity which permits the transfer of between about and about 80 (even more generally 30 to 55) milliliters of water per Faraday of current passing through the membrane, as measured with a current density of 0.5 ampls/cm. in a cell having aqueous 0.5M sulfuric acid in both anolyte and catholyte compartments.
  • a membrane reinforced by two or three sheets of glass fabric is preferably at least about 0.1 centimeter thick for satisfactory rigidity but generally not more than about 0.25 centimeter thick to avoid the undesirable brittleness of a membrane containing too high a proportion of the polymer.
  • FIG. ll schematically illustrates a system in which a membrane of the type shown in FIG. 1 can be employed in the electrohydrodimerization of one or more olefmic nitriles, esters and/or carboxamides.
  • the FIG. ll system includes an anode leaf 6 and a cathode leaf 7 which are assembled together and clamped under sufficient pressure to prevent fluid leakage.
  • Anode leaf 6 has a plate-like anode 8 mounted on its right side and a plate-like cathode 9 is similarly mounted on the left side alloys.
  • the ion-exchange membrane 10 is sealingly clamped between the peripheral portions of anode leaf 6 and cathode leaf 7, separating the space between leaves 6 and 7 into an anode compartment 1 l and a cathode compartment 12.
  • an aqueous anolyte containing an acid such as sulfuric acid is pumped by anolyte pump 13 from surge tank 14 into anode compartment 11 through which it flows upwardly in contact with anode 8 and membrane 10 and thereafter back to tank 14.
  • An aqueous catholyte containing the olefinic nitrile, ester and/or carboxamide and preferably an electrolytic salt e.g., a quaternary ammonium or amine salt such as a tetraalkylammonium alkylsulfate or sulfonate
  • an electrolytic salt e.g., a quaternary ammonium or amine salt such as a tetraalkylammonium alkylsulfate or sulfonate
  • the cell in commercial operation, the cell is run continuously with the dimerization product continuously withdrawn from tank 16, oxygen and other gases allowed to escape from tank i4, and fresh acid and fresh olefmic feed continuously fed to tanks 14 and 16, respectively. It is in such operation that the tendency toward deterioration of the membrane 10 (primarily on the cathode side) is especially pronounced, the need for a consistently long membrane life is critically important, and the deterioration resistance of membranes reinforced by a plurality of sheets of woven glass fabric is unexpectedly great. For example, under normal operating conditions, the service life of such membranes has been generally two or more times the average service life of membranes having only one sheet of glass fabric similarly embedded in a matrix of the same polymeric material.
  • EXAMPLE I Acrylonitrile was continuously electrohydrodimerized to adiponitrile as described hereinbefore in a series of plant-scale cells each utilizing an aqueous sulfuric acid anolyte, tetraethylammonium ethylsulfate as the electrolytic salt in the catholyte and an ion-exchange membrane made of a solid matrix of sulfonated divinylbenzene-styrene copolymer (0.106 cm. thick) reinforced by two substantially parallel sheets of woven 9-ounce 21 X 14 thread count glass fabric embedded within the polymeric matrix by the membrane preparation procedure described hereinbefore.
  • the glass fabrics were made of staple fibers with parallel fiber orientation and the membranes had a porosity which permitted the passage of 32 milliliters of water from anolyte to catholyte per Faraday of electric current transmitted through the membrane, as measured with a current density of 0.5 amps/cm. of membrane surface area in a cell having aqueous 0.5M sulfuric acid in both anoiyte and catholyte compartments.
  • the deterioration of the membranes was determined by measuring the rate of water leakage through each membrane with a hydrostatic differential pressure of 4 p.s.i. on the anolyte in the cell. After the membranes had been in use for 2,200 hours, their average water leakage rate was about 0.2 milliliters per hour per l00 cm. of membrane surface area.
  • EXAMPLE 4 When the procedure of example 1 was repeated with the exception that the membrane contained three sheets of the same type of woven glass fabric and had a thickness of 0.22 cm. and a porosity that pennitted passage of 44 milliliters of water per Faraday of current, there was no measurable water leakage rate after the membranes had been in use for 1,500 hours.
  • COMPARATIVE EXAMPLE A When the procedure of example 1 was repeated with the exception that two back-to-back membranes each containing one sheet of the woven glass fabric and having a porosity that permitted passage of 49 milliliters of water per Faraday of current were used in place of the membrane containing two glass fabric sheets, the average water leakage rate was about 0.2 milliliters per hour after 80 hours, 1.8 milliliters per hour after 575 hours, 2 milliliters per hour after 1,030 hours, and 4 milliliters per hour after the membranes had been in use for 1,600 hours.
  • COMPARATlVE EXAMPLE F When the procedure of example 1 was repeated with the exception that the membranes each contained one sheet of woven Teflon cloth sandwiched between two sheets of nonwoven polypropylene fabric and had a porosity which permitted passage of 38 milliliters of water per Faraday of current, the average water leakage rate was about 1.9 milliliters per hour after 525 hours, 2.1 milliliters per hour after 700 hours, 2.8 milliliters per hour after 1,280 hours, and 4 milliliters per hour after the membranes had been in use for 1,780 hours.
  • FIG. 111 The results of examples l-4 and comparative examples A-I-I are graphically represented in FIG. 111 from which it is readily apparent that the durability of membranes containing at least two sheets of woven glass fabric is significantly greater in the process of this invention than that of ion-exchange membranes having other types of reinforcement in similar process use.
  • FIG. 11] demonstrates that the leakage rate of the other membranes (e.g., those having only one sheet of glass or Teflon fabric, with or without additional reinforcement by nonwoven fabrics) increased during cell service at a rate of at last about seven times the leakage rate of the membranes used in the process of this invention.
  • a process for producing hydrodimers of olefinic compounds which comprises passing electric current through an aqueous olefinic nitrile-, esteror carboxamide-containing catholyte separated from an aqueous acidic anolyte by an ionexchange membrane comprising a solid electrically conductive polymeric cation-permeable matrix reinforced by at least two substantially parallel sheets of fabric embedded within said matrix, all of said sheets being of woven glass fabric.
  • the matrix comprises a copolymer of a polyvinyl aromatic compound an a monovinyl aromatic compound having sulfonic groups chemically bonded to the aromatic nuclei of the copolymer.
  • catholyte contains an electrolytic salt having a discharge potential more negative than that of salt olefinic nitrile, ester or carboxamicle.
  • a process for producing hydrodirners of olefinic compounds which comprises passing electric current through an aqueous olefinic nitrile-, esteror carboxamidecontaining

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US704279A 1968-02-09 1968-02-09 Electrolytic hydrodimerization of olefinic compounds Expired - Lifetime US3616319A (en)

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US (1) US3616319A (de)
JP (1) JPS541687B1 (de)
AT (1) AT287670B (de)
BE (1) BE728204A (de)
BR (1) BR6906260D0 (de)
CA (1) CA920532A (de)
CH (1) CH509985A (de)
DE (1) DE1906545A1 (de)
FR (1) FR2001648A1 (de)
GB (1) GB1257215A (de)
IL (1) IL31582A0 (de)
LU (1) LU57935A1 (de)
NL (1) NL6902080A (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976549A (en) * 1973-02-26 1976-08-24 Hooker Chemicals & Plastics Corporation Electrolysis method
US4164463A (en) * 1975-05-20 1979-08-14 E. I. Du Pont De Nemours And Company Hydrophilic fluoropolymers
DE3029870A1 (de) * 1979-08-10 1981-02-26 Asahi Chemical Ind Verstaerkte kationenaustauscher-membran
US4391663A (en) * 1980-12-05 1983-07-05 Hutter Iii Charles G Method of curing adhesive
US5523181A (en) * 1992-09-25 1996-06-04 Masahiro Watanabe Polymer solid-electrolyte composition and electrochemical cell using the composition
US20120089237A1 (en) * 2009-01-30 2012-04-12 Pekka Vallittu Composite and its use

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976549A (en) * 1973-02-26 1976-08-24 Hooker Chemicals & Plastics Corporation Electrolysis method
US4164463A (en) * 1975-05-20 1979-08-14 E. I. Du Pont De Nemours And Company Hydrophilic fluoropolymers
DE3029870A1 (de) * 1979-08-10 1981-02-26 Asahi Chemical Ind Verstaerkte kationenaustauscher-membran
US4337141A (en) * 1979-08-10 1982-06-29 Asahi Kasei Kogyo Kabushiki Kaisha Cation exchange membrane
US4391663A (en) * 1980-12-05 1983-07-05 Hutter Iii Charles G Method of curing adhesive
US5523181A (en) * 1992-09-25 1996-06-04 Masahiro Watanabe Polymer solid-electrolyte composition and electrochemical cell using the composition
US20120089237A1 (en) * 2009-01-30 2012-04-12 Pekka Vallittu Composite and its use
US9144630B2 (en) * 2009-01-30 2015-09-29 Skulle Implants Oy Composite and its use

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DE1906545C3 (de) 1974-10-31
CH509985A (de) 1971-07-15
IL31582A0 (en) 1969-04-30
CA920532A (en) 1973-02-06
JPS541687B1 (de) 1979-01-27
FR2001648A1 (de) 1969-09-26
DE1906545B2 (de) 1974-04-04
LU57935A1 (de) 1969-09-17
DE1906545A1 (de) 1969-08-28
GB1257215A (de) 1971-12-15
BE728204A (de) 1969-08-11
BR6906260D0 (pt) 1973-01-09
NL6902080A (de) 1969-08-12
AT287670B (de) 1971-02-10

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