US2816936A - Process for formation of dialkali metal dimers of diolefins - Google Patents

Process for formation of dialkali metal dimers of diolefins Download PDF

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Publication number
US2816936A
US2816936A US556469A US55646955A US2816936A US 2816936 A US2816936 A US 2816936A US 556469 A US556469 A US 556469A US 55646955 A US55646955 A US 55646955A US 2816936 A US2816936 A US 2816936A
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sodium
alkali metal
reaction
dispersion
microns
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Virgil L Hansley
Schott Stuart
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Millennium Petrochemicals Inc
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National Distillers and Chemical Corp
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Priority to BE553799D priority Critical patent/BE553799A/xx
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Priority to US556469A priority patent/US2816936A/en
Priority to GB38368/56A priority patent/GB819824A/en
Priority to DEN13117A priority patent/DE1054994B/de
Priority to FR1169067D priority patent/FR1169067A/fr
Priority to CH357064D priority patent/CH357064A/de
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J16/00—Chemical processes in general for reacting liquids with non- particulate solids, e.g. sheet material; Apparatus specially adapted therefor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a process for prod'ucwith a substantial excess of sodium in the presence of tion of dimerized products from diolefins and, more parethylene glycol dirnethyl ether or dimethyl ether with ticularly, to a process wherein a conjugated aliphatic the solid sodium surface 'being continually abraded durdiolefin is reacted with an alkali metal to produce, in ing the reaction by forcing the sodium against a wire selective manner and high yields, dimerized products of brush.
  • the conditions under which the studies were carthe diolefin.
  • the invention relates to ried out and the results obtained are set forth in the folan improved process wherein an aliphatic conjugated dilowing tabulation and include results obtained with simulolefin such as butadiene, is selectively dimerized in the taneous or subsequent carbonation of the reaction prodpresence of a finely divided alkali metal, such a sodium, uct.
  • a finely divided alkali metal such as sodium, uct.
  • Patent No. 2,352,461 to prepare mixtures of organic disclosed in co-pending application S. N. 382,456, filed acids by reacting an aliphatic diolefin such as butadiene, with sodium or potassium and carbon dioxide in a special solvent and to hydrolyze the compounds so obtained.
  • This patent discloses the use of sodium in massive form (i. e., sodium strips) for carrying out the described reaction with or without provision for abrading or scraping the sodium surface, such as with a rotating brush or scraper, to remove continuously encrustations from the sodium and expose fresh surfaces of the metal.
  • Average particle size About 12 microns. Maximum particle size About 30 microns. Percent of particles of about microns or less Not more than about 10. Percent of particles above about microns Do.
  • reaction of an aliphatic conjugated diolefin such as butadiene, in the presence of the selected ether reaction mediums, with an alkali metal such as sodium in bulk form or in the form of a dispersion of sodium particles as fine as aforedefined for the Normal dispersion results in no substantial, if any, production of dimerized butadiene derivatives convertible to C diacids
  • the reaction with use of such Normal dispersions can be carried out with selective high yields of desired disodiooctadienes carbonatable to salts of C aliphatic diacids by processes described in co-pending applications S. N. 333,354, filed January 26, 1953, now abandoned; S. N. 382,456, filed September 25, 1953, and S. N.
  • desiderata are the production of such derivatives in selective manner and in high yields with minimization of the number of required ingredients in the mixture undergoing dimerization and facilitation of subsequent handing operations, which are complicated by the presence of certain ingredients, in the: conversion of the reaction product to, and recovery of, desired valuable derivatives of the dimerized product.
  • desiderata include the provision of a method for reacting a conjugated diolefin with an alkali metal under conditions for selective production in high yields of dialkali metal derivatives of the diolefin dimers without need for use of any activating agents, attrition agents, and the like, thereby simplifying the entire process by substantial reduction in the number of ingredients required and thereby obviating problems associated with the presence of activating agents, etc. in the preparation and recovery of the dialkali metal dimers and/or desired derivatives thereof.
  • an aliphatic conjugated diolefin can be reacted with an alkali metal in the presence of a selected reaction medium to produce, in selective manner and in high yields, dialkali metal derivatives of dimers of the diolefin if the alkali metal reactant is employed in the form of a dispersion in which the particle size characteristics of the dispersed alkali metal fall within rather well defined limits of size characteristics.
  • average particle size characteristics of the alkali metal dispersion is not necessarily the sole factor which enables carrying out the invention as, over and above average size characteristics, it is essential that the alkali metal dispersion contain in excess of a rather well defined amount of relatively low size characteristics.
  • the desired dimerization reaction can be effected by use of an alkali metal dispersion of particle size characteristics as embodied for use herein whereas the desired dimerization may not be effected by use of an alkali metal dispersion which, though it may be of comparable average particle size characteristics, does not contain the rather well defined amount of particles of controlled size characteristics required for practice of the present invention.
  • the process embodied herein comprises reacting an aliphatic conjugated diolefin, in the presence of a suitable reaction medium, with an alkali metal in dispersed form in which more than about 30% of the alkali metal particles are of less than about five microns in size, and more preferably, not more than about three microns in size, under conditions whereby there is produced in selective manner high yields of dialkali metal derivatives of dimers of the diolefin.
  • the process embodied herein is carried out by use of the alkali metal in the form of a dispersion in which more than about 30% of the alkali metal particles are of less than about five microns in size, and more preferably, not over about three microns, and the average particle size of the dispersion is not more than about ten microns.
  • the invention is carried out by use of the alkali metal in the form of a dispersion in which (a) more than about 30% of the alkali metal particles do not exceed about three microns in size,-
  • the average particle size of the dispersion averages not more than about one micron and (c) the dispersion is devoid of more than about of alkali metal particles larger than about fifteen microns in size.
  • Optimum results are generally obtained by use of an alkali metal dispersion in which all or substantially all of the alkali metal particles do not exceed about three microns in size and the average particle size is less than 1 micron in diameter.
  • suitable examples of the alkali metal include sodium, potassium and lithium with sodium being preferred as it provides for excellent selectivity and yields of desired dimerized products and is cheaper and more readily available.
  • Use of chemically pure sodium is not essential, however, as mixtures containing a substantial amount of sodium are useful as are alloys of sodium and potassium, of sodium and calcium, and of sodium and lithium.
  • the diolefins which are useful for this improved process include any aliphatic conjugated diolefin including, for example, butadiene, isoprene, dimethyl butadiene, the pentadienes, as the methyl-1,3-pentadienes, and the like. In general, it is desirable to use the aliphatic conjugated diolefins having from 4 to 8, inclusive, carbon atoms.
  • the reaction medium found most suitable consists essentially of an ether and only certain types of ethers are effective.
  • the ether can be any aliphatic mono ether having a methoxy group, in which the ratio of the number of oxygen atoms to the number of carbon atoms is not less than 1:4. Examples include dimethyl ether, methyl ethyl ether, methyl n-propyl ether, methyl isopropyl ether, and mixtures of these methyl ethers.
  • Certain aliphatic polyethers are also quite satisfactory. These include the acyclic and cyclic polyethers which are derived by replacing all of the hydroxyl hydrogen atoms of the appropriate polyhydric alcohol by alkyl groups.
  • Typical examples are the ethylene glycol dialkyl ethers such as the dimethyl, methyl ethyl, diethyl, methyl butyl, ethyl butyl, dibutyl, and butyl lauryl ethylene glycol ethers; trimethylene glycol dimethyl ether, glycerol trimethyl ether, glycerol dimethyl ethyl ether, and diethylene glycol methyl ethyl ether, dioxane, glycol formal, methyl glycerol formal, and the like, as well as ethyl and methyl ortho formates, methylal and acetals having the proper carbon to oxygen ratio.
  • the simple methyl monoethers, as dimethyl ether, and the polyethers of ethylene glycols, as ethylene glycol dimethyl ether are preferred.
  • Hydrocarbon solvents such as isooctane, kerosene, toluene, and benzene cannot be used exclusively as reaction media since they adversely affect the dimerization reaction and give little or no yield of dimer products.
  • the ethers should not contain any groups such as hydroxyl, carboxyl, and the like which are distinctly reactive towards sodium. Although the ether may react in some reversible manner, it must not be subject to cleavage to give irreversible reaction products during the dimerization process. Such cleavage action destroys the ether and introduces into the reacting system metallic alkoxides which, in turn, tend to induce the rubber forming reaction with the diolefin rather than the desired dimerization reaction.
  • reaction medium should consist essentially of the specified ethers
  • other inert media can be employed in limited amounts.
  • these inert media will be introduced with the alkali metal dispersion as the vehicles in which the alkali metal is suspended. They have the principal effect of diluting the ethers.
  • the effective concentration of the active ether is decreased by the increased addition of inerts, a minimum concentration of ether is reached below which the promoting effect is not evident. The exact minimum concentration depends upon the particular reactants and ether being used as well as the reaction conditions, such as temperature,
  • the concentration of ether in the reaction mixture should at all times be maintained at a sufficient level to have a substantial promoting effect upon the dimerization reaction.
  • dispersing agents capable of promoting rapid and complete breakdown of the gross sodium particles.
  • Choice of these dispersing aids is important, although a number of different selected materials can be used.
  • copper oleate is used for maximum rapid particle breakdown, and dimer acid for maximum dispersion stability.
  • Aluminum stearate, as well as other selected metallic soaps have also been found to function quite satisfactorily.
  • other materials can also be used either alone or in combinations.
  • Dispersing aids which are useful include dimer acid, oleic acid, aluminum stearate, aluminum octanoate, calcium stearate, aluminum laurate, lead naphthenate, zinc stearate and other metallic soaps as well as lecithin, polymers, rubbers, etc.
  • the reaction temperature is preferably held below 0 C., and more preferably, between 20 C. to -50 C. as generally speaking, all ethers begin to yield cleavage products at temperatures of about 0 C. and above with the result that sufiicient alkoxides are formed to yield high polymeric acids rather than the desired low molecular weight dimers.
  • the reaction may be carried out at somewhat higher temperatures, with or without use of pressure, such as up to about 30 C., but use of the higher temperatures are generally not preferred as the yield of desired products tends to decrease as the temperature is increased over about 0 C.
  • the process embodied herein may be carried out in batch-wise, semi-continuous or continuous manner and it is not intended to be limited to any particular method of operation.
  • the reaction may be carried out in a stirred reaction vessel in which the ether reaction medium and alkali metal dispersion are maintained at desired temperature (e. g., below about 0 C.) and the diolefin reactant introduced either as a gas, or as a liquid.
  • desired temperature e. g., below about 0 C.
  • the diolefin reactant introduced either as a gas, or as a liquid.
  • desired temperature e. g., below about 0 C.
  • the diolefin reactant introduced either as a gas, or as a liquid.
  • One quite satisfactory method is to introduce the diolefin into the reaction vessel at approximately the same rate at which it reacts with the alkali metal.
  • finely dispersed alkali metal it is usually suitable to employ only an equimolar amount with the o
  • the dimetallic derivatives of the diolefin dimers which are selectively formed are thus produced in the reaction mixture.
  • These products depending on the diolefin used, may be either soluble or insoluble in the reaction medium. In general, they tend to form slurries, as for example, the disodiooctadienes produced from sodium and butadiene.
  • dimetallo derivatives can either be isolated as such or directly and immediately thereafter subjected to further reactions to form valuable derivatives.
  • subsequent carbonation of the mixture containing the products yields the salts of dicarboxylic acids.
  • the carbonation may be carried out by subjecting the dimetallo derivatives to dry, gaseous carbon dioxide, by contact with solid carbon dioxide or by means of a solution of carbon dioxide.
  • the temperature for carbonation is preferably controlled below about 0 C. to avoid the formation of unwanted by-products.
  • the carbonation forms the dimetallic salts of the unsaturated aliphatic dicarboxylic acids, containing two more carbon atoms per molecule than the dimers from which they are produced. In the case, for example, where butadiene is the starting aliphatic diolefin, there results by such a method 7 n the selective production of C unsaturated aliphatic dicarboxylic acids.
  • the unsaturated diacid products find use as chemical intermediates, and are valuble in the preparation of polymers and copolymers, plasticizers, and drying oils. They, as well as certain derivatives, are useful in esters, polyester and polyamide resins and, generally, as chemical intermediates.
  • the unsaturated diacids or their salts or other derivatives can be hydrogenated at the double bonds to yield the corresponding saturated compounds, particularly the saturated diacids.
  • This also affords a convenient and accurate way to identify structures of the intermediate products.
  • the disodiooctadiene product obtained from reaction of butadiene with sodium by a process embodied herein ultimately yields a practically quantitative mixture of sebacic acid, 2-ethylsuberic acid, and 2,2-diethyladipic acid upon subjecting the disodiooctadiene product to carbonation, hydrogenation and acidification.
  • an inert hydrocarbon is placed in a suitable vessel with the appropriate amount of alkali metal (sodium), suitable materials useful as the inert hydrocarbon being saturated dibutyl ether, n-octane, isooctane, toluene, xylene, naphthalene, n-heptane, straight run kerosenes, etc.
  • suitable materials useful as the inert hydrocarbon being saturated dibutyl ether, n-octane, isooctane, toluene, xylene, naphthalene, n-heptane, straight run kerosenes, etc.
  • the mixture is then heated in a surrounding bath or otherwise until the sodium has melted M. P. 97.5" C).
  • a suitable high speed agitator is then started and, preferably, an emulsifier consisting, for example of /2% (based on sodium) of the dimer of linoleic acid is added.
  • an emulsifier consisting, for example of /2% (based on sodium) of the dimer of linoleic acid is added.
  • a dispersion of sodium particles in the range of 5-15 microns is normally obtained (i. e., Normal dispersions illustrative of finely dispersed sodium which, for obtaining substantial yields of the desired dimerized products, require use of an activating agent and/or attrition agent as aforedescribed in reaction with the diolefin).
  • a suitable mill such as a homogenizer, is preheated by placing a small amount of inert hydrocarbon (e. g., mineral spirits) in the retention pot and running the mill until the liquid reaches a temperature in the range of 105-1 C.
  • a temperature in the range of 105-1 C.
  • the above described preformed Normal dispersion is added to the retention pot while the mill is continued in operation.
  • the vehicle for the dispersion and the small amount used for pre-heating the homogenizer mill are calibrated and accounted for so that a sodium concentration of from about 10 to about 60%, and preferably -50%, is maintained for preparation of final finished dispersions of highly suitable stability characteristics.
  • the selective dispersing aid or aids that are employed can be incorporated by adding only a portion of the total amount thereof to the mixture while forming addition thereto of the Normal dispersion.
  • all of the dispersing aids can be added to the preformed dispersion before its addition to the homogenizer equipment.
  • the Normal dispersions can be converted to dispersions in which the maximum size of the particles of sodium do not exceed about 3 microns with an average micron size of l and less and which, for purposes herein are designated as the Fine dispersions utilized in describing specific embodiments of the invention.
  • other dispersion units including those of the ultrasonic type, may be used and which operate successfully with either a preformed dispersion or molten sodium feed.
  • the sodium dispersions employed in the runs for which data are shown consisted of a Normal dispersion itself, a Fine dispersion sodium) prepared as aforedescribed in mineral spirits, and controlled mixtures of such dispersions, the particle size characteristics of which were determined by visual examination with a microscope hav ing a calibrated eyepiece.
  • the reactions, for which data are set forth in the following tabulation, were carried out in a stirred reactor having a gas inlet tube and a reflux condenser vented to a nitrogen atmosphere. The reactor system was purged with nitrogen and charged with 3 liters of 'dimethyl ether, followed by addition of the sodium dispersion (1.1 g. atoms). Butadiene (l g.
  • the use of alkali metal dispersions as embodied for use herein, obviates or substantially minimizes the agglomeration or lump-forming tendency of dispersed sodium, the occurrence of which requires, while carrying out reactions therewith, more frequent shutdowns due to plug-up of equipment, transfer lines, etc.
  • a process for selective formation of dialkali metal dimers of a conjugated aliphatic diolefin which comprises reacting a conjugated aliphatic diolefin with finely divided particles of an alkali metal dispersed in an ether reaction medium from the group consisting of aliphatic monoethers having a methoxy group and an oxygen to carbon ratio of not less than 1:4 and polyethers derived from an aliphatic polyhydric alcohol having all the hydroxyl hydrogen atoms replaced by alkyl groups and mixtures thereof, said finely divided alkali metal being comprised of particles of which more than about 30% are less than about five microns in size and the average particle size of the alkali metal particles is substantially less than eight microns.
  • a process for selective formation of dialkali metal dimers of a conjugated aliphatic diolefin which comprises reacting a conjugated aliphatic diolefin with finely divided particles of an alkali metal dispersed in a liquid ether reaction medium from the group consisting of aliphatic monoethers having a methoxy group and an oxygen to carbon ratio of not less than 1:4 and polyethers derived from an aliphatic polyhydric alcohol having all the hydroxyl hydrogen atoms replaced by alkyl groups and mixtures thereof, said finely divided alkali metal being comprised of particles of which more than about 30% are not more than about three microns in size and the average particle size of the finely divided alkali metal is not more than about six microns.
  • the alkali metal is sodium
  • the diolefin is butadiene
  • substantially all of the dispersed sodium particles are not more than about three microns in size
  • the average particle size of the dispersed sodium is not more than about one micron
  • the reaction is carried out at a temperature not in excess of about 0 C.
  • the ether reaction medium is dimethyl ether.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US556469A 1955-12-30 1955-12-30 Process for formation of dialkali metal dimers of diolefins Expired - Lifetime US2816936A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BE553799D BE553799A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1955-12-30
US556469A US2816936A (en) 1955-12-30 1955-12-30 Process for formation of dialkali metal dimers of diolefins
GB38368/56A GB819824A (en) 1955-12-30 1956-12-17 Improvements in or relating to the preparation of dialkali metal derivatives of dimerized aliphatic conjugated olefines
DEN13117A DE1054994B (de) 1955-12-30 1956-12-21 Verfahren zur Herstellung der Dialkaliderivate dimerer Diolefine mit konjugierten Doppelbindungen
FR1169067D FR1169067A (fr) 1955-12-30 1956-12-26 Procédé de fabrication de produits dimérisés
CH357064D CH357064A (de) 1955-12-30 1956-12-29 Verfahren zur Herstellung von Dialkaliverbindungen dimerer konjugierter Diolefine

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CH (1) CH357064A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE1054994B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2954410A (en) * 1957-07-31 1960-09-27 Nat Distillers Chem Corp Metalation process
US2999109A (en) * 1958-03-05 1961-09-05 Nat Distillers Chem Corp Preparation of cyclopentadienylsodium
US3388178A (en) * 1963-12-27 1968-06-11 Lithium Corp Preparation of solutions of lithium-conjugated polyene hydrocarbon adducts

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1177157B (de) * 1960-11-21 1964-09-03 Phillips Petroleum Co Verfahren zur Herstellung von lithiumorganischen Verbindungen

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2352461A (en) * 1942-02-25 1944-06-27 Du Pont High molecular weight unsaturated organic acids and process of preparing them
US2579257A (en) * 1949-03-17 1951-12-18 Du Pont Alkali metal dispersions
US2773092A (en) * 1954-12-06 1956-12-04 Ethyl Corp Dimerization process
US2799705A (en) * 1952-06-11 1957-07-16 Ethyl Corp Substituted sodium amides

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2816916A (en) * 1953-01-26 1957-12-17 Nat Distillers Chem Corp Dimerization process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2352461A (en) * 1942-02-25 1944-06-27 Du Pont High molecular weight unsaturated organic acids and process of preparing them
US2579257A (en) * 1949-03-17 1951-12-18 Du Pont Alkali metal dispersions
US2799705A (en) * 1952-06-11 1957-07-16 Ethyl Corp Substituted sodium amides
US2773092A (en) * 1954-12-06 1956-12-04 Ethyl Corp Dimerization process

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2954410A (en) * 1957-07-31 1960-09-27 Nat Distillers Chem Corp Metalation process
US2999109A (en) * 1958-03-05 1961-09-05 Nat Distillers Chem Corp Preparation of cyclopentadienylsodium
US3388178A (en) * 1963-12-27 1968-06-11 Lithium Corp Preparation of solutions of lithium-conjugated polyene hydrocarbon adducts

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FR1169067A (fr) 1958-12-22
GB819824A (en) 1959-09-09
DE1054994B (de) 1959-04-16
CH357064A (de) 1961-09-30
BE553799A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

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