US2816916A - Dimerization process - Google Patents

Dimerization process Download PDF

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US2816916A
US2816916A US382456A US38245653A US2816916A US 2816916 A US2816916 A US 2816916A US 382456 A US382456 A US 382456A US 38245653 A US38245653 A US 38245653A US 2816916 A US2816916 A US 2816916A
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diolefin
sodium
aliphatic
butadiene
ether
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Charles E Frank
Walter E Foster
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Millennium Petrochemicals Inc
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National Distillers and Chemical Corp
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Priority to US382456A priority Critical patent/US2816916A/en
Priority to FR1093096D priority patent/FR1093096A/fr
Priority to CH331850D priority patent/CH331850A/fr
Priority to DEN8358A priority patent/DE1150679B/de
Priority to CH327718D priority patent/CH327718A/fr
Priority to CH322988D priority patent/CH322988A/fr
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/13—Dicarboxylic acids
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated

Definitions

  • This invention relates broadly to a novel process for the preparation of dimerized products from dienes and to the compositions obtained thereby and, more specifically, relates to a process wherein conjugated aliphatic diolefins are selectively reacted to give high yields of dimerized derivatives relatively free from more highly polymerized products.
  • Another object of this invention is to carry out a subsequent step by carbonating the dimetallo derivatives so obtained to form the salts of dicarboxylic acids derived from the dimerized dienes and having two additional carbon atoms.
  • the resulting salt products may be converted to acids and the latter isolated, or the salt products may be separated as such and then converted to acids.
  • a further, more specific object is to selectively dimerize butadiene using finely dispersed sodium and in the presence of an ether reaction medium and a small amount of a polycyclic-aromatic hydrocarbon to obtain disodiooctadienes and, if desired, thereafter to carbonate said product to obtain aliphatic C dicarboxylic acids and salts thereof.
  • the present invention is carried out by initially treating an aliphatic conjugated diolefin with finely dispersed sodium or potassium in the liquid ether medium and in the presence of a relatively small amount of a polycyclic aromatic hydrocarbon at a temperature below C.
  • the disodiodiene product thus obtained is then carbonated at a temperature below 0 C., to give the salts of the desired dicarboxylic acids in high yields and selectivity.
  • the net result of the initial step is a reaction which yields a dimerized product.
  • this product comprises the disodium derivatives of the aliphatic octadienes. From a study of structures of the saturated diacids arising therefrom, it has nited States Patent I 2,816,916 Patented Dec. 17, 1957 'ice Using the herein described selective process, it is possible to obtain combined yields of the above C dimerized products ranging up to -90%based on the butadiene.
  • the diolefins which are useful for this improved process include any aliphtic conjugated diolefin such as, for example, butadiene, isoprene, dimethyl butadiene, the pentadiens, as the methyl-1,3-pentadienes, and the like.
  • aliphtic conjugated diolefin such as, for example, butadiene, isoprene, dimethyl butadiene, the pentadiens, as the methyl-1,3-pentadienes, and the like.
  • the meth- 001 is particularly well adapted to the use of butadiene as the diolefin.
  • Either sodium or potassium may be used as the alkali metal reactant.
  • the use of sodium is preferred over potassium since sodium gives'excellent selectivity and yields of dimerized products, and it is cheaper and more readily available.
  • Chemically pure sodium is not essential, however, since mixtures containing a major proportion of sodium are also useful.
  • alloys of sodium and potassium, sodium and calcium, and sodium and lithium can be used.
  • a sodium dispersion in which the average particle size is less than 50 microns is necessary for satisfactory dimerization since bulk sodium instead of dispersed sodium either yields no product or results largely in the formation of highly condensed diene polymers.
  • the formation of these unwanted polymeric products as the major reaction product can be substantially avoided by employing the sodium or potassium as a fine dispersion.
  • This dispersion is most conveniently made in an inert hydrocarbon or ether as a separate step preliminary to the reaction with the diene.
  • the reaction medium found most suitable consists essentially of an ether and only certain types of ethers are effective. These particular classes of ethers have the common property of serving as promoters of the diolefin dimerization.
  • 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.
  • 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 diethyI, 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 bydroxyl, 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
  • these inert media will be introduced with the sodium dispersion as the liquid in which the sodium 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, reactant concentration, and the like employed. In any event, the concentration of ether in the reaction mixture should at all times be maintained at a sufficient level to have a substantial promoting eifect upon the dimerization reaction.
  • reaction medium having at least 50 wt. percent of active ether. Although the amount may be varied considerably, from 100 to 2000 cc. of the ether per mole of diolefin undergoing reaction has been found satisfactory.
  • a relatively small amount of at least one compound of the polycyclic aromatic class it is intended to include condensed ring hydrocarbons such as naphthalene and phenanthrene, as well as the uncondensed polycyclic compounds such as diphenyl, the terphenyls, dinaphthyl, tetraphenyl ethylene and the like. It is also intended to include mixtures of these compounds.
  • the polyphenyl compounds such as diphenyl and the terphenyls and their mixtures have been found to be particularly useful.
  • the amount of the hydrocarbon required will vary over a range which in every case will be relatively small in comparison with the amount of diolefin undergoing reaction. The exact amount in any particular reaction will depend on temperature, time of reaction and the structure of the diolefin. Concentrations in the range of 0.1 to wt. percent based on the amount of diolefin are ordinarily quite sufiicient.
  • active hydrocarbons have the property of yielding highly colored sodium hydrocarbon addition products in the presence of the active ether employed. While the exact role played by such materials is not fully understood and it is not desired to limit the process to an exact theory, they can be regarded as chemical activating agents which, in effect, have the property of transferring metallic sodium to the diolefin in the reaction zone, facilitating its passage through a film of sodium reaction product which would ordinarily effectively isolate the sodium from reagents present in solution in the surrounding medium.
  • the addition of butadiene to an ether solution of sodium-terphenyl in the absence of metallic sodium yielded little or no dimerized butadiene products, but only condensed ring products derived from terphenyl. Therefore, this process is not equivalent to the use of a metallic derivative'of the polycyclic aromatic compound as the dimerization agent.
  • reaction temperature preferably be held below 0 C.
  • the temperature range between -20 to --50 C. is the preferred one.
  • 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 disodio-diolefin dimers.
  • the reaction may be carried out in a stirred reaction vessel.
  • the sodium or potassium dispersion is initially prepared by placing an inert hydrocarbon such as isooctane in a suitable vessel with the appropriate weigh-t of sodium. Using finely dispersed sodium it is only necessary to employ an equimolar amount with the butadiene to be reacted. Although a slight excess may be added, it is unnecessary and it is desirable to have no unconsumed metal remaining at the end of the reaction period. The mixture is heated in a surrounding bath or otherwise until the sodium has melted (M. P. 97.5 0).
  • a suitable high speed agitator is 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 test sample of the dispersion shows the particle size to be in the 5-15 micron range.
  • the stirring is stopped and the dispersion is allowed to cool to room temperature.
  • This dispersion is now ready to be used in the selective dimerization of diolefins.
  • Inert liquids such as saturated dibutyl ether, normal octane, n-heptane, or straight run kerosenes, may be employed as suspension media for the dispersion. Any such dispersion having sufficiently finely divided sodium or potassium will suffice.
  • Other well-known substances may be used instead of the dimeric linoleic acid as the dispersing
  • the dispersion is cooled to and maintained below 0 C. and the diolefin introduced either as a gas, or under pressure, in the liquid phase.
  • the diolefin introduced either as a gas, or under pressure, in the liquid phase.
  • One quite satisfactory method is to introduce the diolefin into the reaction vessel at approximately the same rate as that at which it reacts with the sodium.
  • This reaction may be carried out either in a batchwise or in a continuous manner and it is not intended to limit the process to any particular method of operation.
  • the dimetallic derivatives of the diolefin dimers which are selectively formed are thus produced in the reaction mixture.
  • These products depending on the diolefin, may be either soluble or insoluble in the reaction medium. In general, they tend to form slurries, as for example, the disodiooctadiene produced from sodium and butadiene.
  • these dimetallic derivatives are in themselves novel and it is intended to claim them as new compositions of matter. They can either be isolated as such, or, since they tend to be unstable and diflicult to handle, they can be directly and immediately thereafter subjected to further reactions to form valuable derivatives. For example, subsequent carbonation of the mixture containing the products yields the salts of dicarboxylic acids.
  • the carbonation may be done by subjecting the dimetallic-diene derivatives to dry gaseous carbon dioxide, by contact with solid carbon dioxide or by means of a solution of carbon dioxide. The temperature should be controlled below 0 C. to avoid the formation of unwanted by-products. This carbonation forms the dimetallic salts of the unsaturated aliphatic dicarboxylic acids.
  • salts will contain two more carbon atoms than the dimetallic diene dimers from which they are produced.
  • butadiene is the starting aliphatic diolefin, there results by this method the selective production of C unsaturated dicarboxylic acids.
  • the dimetallic diene dimer is first made and the carbonation is done as soon afterwards as possible. If carbon dioxide is present during the dimerization, the reaction is neither as selective nor as complete.
  • the diacid salts are water soluble and may easily be separated by a water extraction. Alternatively, they may be converted to the free acids by acidification and separated by filtration, evaporation and/or solvent extraction.
  • 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 butadiene ultimately yields a practically quantitative mixture of sebacic acid, 2-ethyl suberic acid and 2,2-diethyl adipic acid. Traces of 3-ethyl suberic acid also may be present.
  • EXAMPLE 1 Preparation of C diacids from butadiene The reaction was carried out in a stirred reactor having a gas inlet tube extending into the body of the reaction mixture and a reflux condenser vented to a nitrogen atmosphere. This reactor system was purged with nitrogen and charged with 1000 parts of dimethyl ether, 3 parts (about 1.8 wt. percent based on the butadiene used) of para-terphenyl and 69 parts of sodium dispersed in 70 parts of isooctane. The average particle size of the sodium was microns. A stream of gaseous butadiene amounting to a total of 162 parts was passed into the reactor over a 4-hour period While maintaining vigorous agitation and maintaining the reaction temperature at about C. During this period the disodium derivatives of the C butadiene dimers were formed.
  • the reaction mixture containing the disodium derivatives as a slurry was carbonated by pouring it upon an excess of solid carbon dioxide. After evaporation of excess CO dimethyl ether and isooctane, a solid product, consisting essentially of the sodium salts of the C unsaturated dicarboxylic acids remained. A small amount, less than 5%, of rubbery butadiene polymer was also isolated. An alkaline solution of the dicarboxylic acids was hydrogenated using a nickel catalyst.
  • the mixed terphenyls (ortho, meta and para isomers) can be satisfactorily substituted for the para-terphenyl of Example 1. Substantially the same results and products are obtained.
  • EXAMPLE 6 Preparation of C diacids using para-terphenyl An experiment similar to Example 1 was carried out using substantially the same apparatus as that used in Example 1. The reactor was purged with nitrogen and charged with 320 parts of ethylene glycol diethyl ether and 2 parts of para-terphenyl (about 7.4 wt. percent based on the butadiene used). A dispersion of 25 parts sodium. in 50 parts of di-n-butyl ether, in which the sodium had an average particle size of 12 microns, was then added. A stream of butadiene totaling 27.1 parts was then passed into the reactor over a period of six hours while maintaining the temperature of the reacting mixture between 25 and 35" C.
  • Example 6 increased percentages of distillable acids, but, when these was carmfd out s 2 Parts 9 ortho'terphenyl arld were fractionated and studied, they were found to consist Pa of dISPeTSPd Sodlum- A Yleld of 66% of 10 dlbaslc largely of high molecular weight acidic products.
  • dISPeTSPd Sodlum- A Yleld of 66% of 10 dlbaslc largely of high molecular weight acidic products.
  • EXAMPLE 3 shows dicarboxylic EXAMPLE 3 products of 345 to 540.8 molecular weight (neutralization Preparation of C diacids using naphthalene equlvalent X assllmmg dlaclds)- The total Ylelds Of A th these polymeric acids ranged from 53.3% to 56.9%, E n expgnment was earned out ldentlcal with at of based on the butadiene.
  • This ortho-terphenyl-sodium solution was diluted with an additional cc. of the diethyl ether of ethylene glycol. Butadiene (0.68 mole) was then passed into this diluted mixture over a three-hour period at a temperature of 30- C.
  • the clear solution obtained after centrifuging was distilled to give 45 g. of a solid.
  • the original solid was carbonated, then treated with water and free acid. Less than 0.5 g. of organic acids was obtained.
  • An extraction with dibutyl ether gave a large amount of a crystalline solid.
  • the total amount of solids obtained was equivalent to a practically theoretical yield of non-acid material consisting substantially of triphenylene; M. P. after recrystallization, 197-199 C.; M. P. of picrate, ZZZ-224 C.; literature values, 198.5 and 223, respectively.
  • a process which comprises selectively reacting an aliphatic conjugated diolefin with a finely divided alkali metal in an ether reaction medium of 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 in the presence of a small amount, based on the weight of the diolefin, of a polycyclic aromatic hydrocarbon at a temperature below about C., thereby selectively forming the corresponding dialkali metal derivatives of unsaturated hydrocarbon dimers of said diolefin.
  • polycyclic aromatic hydrocarbon is selected from the group consisting of para-terphenyl, ortho-terphenyl, naphthalene, phenanthrene, and mixed terphenyls.
  • aliphatic conjugated diolefin is selected from the group consisting of butadiene, isoprene, and methyl pentadiene.
  • a process for selective preparation of disodio dimers of butadiene which comprises reacting a butadiene containing stream with finely dispersed sodium having an average particle size of below about 50 microns in a reaction medium consisting substantially of dimethyl ether in the presence of from about 0.1 to about 10 weight percent, based on the butadiene, of a polycyclic aromatic hydrocarbon at a temperature below about 0 C., thereby selectively forming disodio dimers of butadiene.
  • a process for selective preparation from an aliphatic conjugated diolefin of dialkali metal salts of aliphatic unsaturated diacids having two more carbon atoms per molecule than a dimer of the diolefin which comprises an initial step of reacting an aliphatic conjugated diolefin with a finely divided alkali metal in an ether reaction medium of 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 in the presence of a small amount, based on the weight of the diolefin, of a polycyclic aromatic hydrocarbon at a temperature below about 0 C.
  • reaction mixture comprising selectively formed dialkali metal derivatives of the unsaturated hydrocarbon dimers of said diolefin, and in a subsequent step carbonating dialkali metal derivatives produced in said initial step and unseparated from said reaction mixture to convert said derivatives to the corresponding dialkali metal salts of aliphatic unsaturated dicarboxylic acids having two more carbon atoms per molecule than a dimer of said diolefin.
  • polycyclic aromatic hydrocarbon is selected from the group consisting of para-terphenyl, ortho-terphenyl, mixed terphenyls, naphthalene and phenanthrene.
  • a process, as defined in claim 7, wherein the aliphatic conjugated diolefin is selected from the group consisting of butadiene, isoprene, and methyl pentadiene.
  • a process for selective preparation from butadiene of disodio salts of C aliphatic unsaturated diacids which comprises an initial step of reacting a butadiene containing stream with finely dispersed sodium having an average particle size of below about 50 microns in a reaction medium consisting substantially of dimethyl ether in the presence of from about 0.1 to about 10 weight percent, based on the butadiene, of a polycyclic aromatic hydrocarbon at a temperature below about 0 C.
  • reaction mixture comprising selectively formed disodio derivatives of dimers of butadiene, and in a subsequent step contacting with carbon dioxide disodio derivatives of dimers of butadiene produced in said initial step and unseparated from said reaction mixture at a temperature below about 0 C. to convert said derivatives to disodio salts of aliphatic unsaturated C dicarboxylic acids.
  • polycyclic aromatic hydrocarbon is selected from the group consisting of para-terphenyl, ortho-terphenyl, naphthalene, diphenyl and phenanthrene.

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US382456A 1953-01-26 1953-09-25 Dimerization process Expired - Lifetime US2816916A (en)

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Application Number Priority Date Filing Date Title
US382456A US2816916A (en) 1953-01-26 1953-09-25 Dimerization process
FR1093096D FR1093096A (fr) 1953-01-26 1954-01-25 Dimérisation des dioléfines et produits obtenus
CH331850D CH331850A (fr) 1953-01-26 1954-01-26 Procédé de préparation sélective des sels dialcalins d'acides dicarboxyliques non saturés
DEN8358A DE1150679B (de) 1953-01-26 1954-01-26 Verfahren zur Herstellung von Dialkylverbindungen von dimerisierten Diolefinen
CH327718D CH327718A (fr) 1953-01-26 1954-01-26 Procédé de préparation sélective d'acides dicarboxyliques saturés
CH322988D CH322988A (fr) 1953-01-26 1954-01-26 Procédé de préparation de dimérisats de dioléfines conjuguées.

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Cited By (9)

* Cited by examiner, † Cited by third party
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US2956087A (en) * 1958-12-04 1960-10-11 Nat Distillers Chem Corp Dimerization of vinyl aromatic compounds
US3012986A (en) * 1959-07-09 1961-12-12 Nat Distillers Chem Corp Urea-formaldehyde modification of branched chain polyamides and product obtained thereby
US3013071A (en) * 1957-12-02 1961-12-12 Nat Distillers Chem Corp Diolefin dimers and acid derivatives thereof
US3061582A (en) * 1959-07-09 1962-10-30 Nat Distillers Chem Corp Ethylenic modification of branched chain polyamides
US3061581A (en) * 1959-07-09 1962-10-30 Nat Distillers Chem Corp Vinyl modification of branched chain polyamides
US3243287A (en) * 1962-09-14 1966-03-29 Crucible Steel Co America Hot strength iron base alloys
US3686299A (en) * 1968-01-31 1972-08-22 Montedison Spa Process for the preparation of acyclic dicarboxylic acids from dienic hydrocarbons
US3716594A (en) * 1969-04-01 1973-02-13 Nippon Soda Co Process for the production of living oligomer
US4034000A (en) * 1963-09-23 1977-07-05 The Goodyear Tire & Rubber Company Difunctional polymeric dienes

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US2773092A (en) * 1954-12-06 1956-12-04 Ethyl Corp Dimerization process
US2858337A (en) * 1955-11-03 1958-10-28 Nat Distillers Chem Corp Method for separating a c10 straight chain aliphatic diacid from mixtures with isomers thereof
US2822389A (en) * 1955-11-15 1958-02-04 Nat Distillers Chem Corp Separation of c10 dicarboxylic acids
US2837564A (en) * 1955-11-15 1958-06-03 Nat Distillers Chem Corp Selective decarboxylation process
US2816919A (en) * 1955-11-23 1957-12-17 Nat Distillers Chem Corp Method of preparing acyclic carboxylic acids
US2816918A (en) * 1955-11-23 1957-12-17 Nat Distillers Chem Corp Carbonation method
BE553799A (fr) * 1955-12-30
US2867656A (en) * 1956-03-27 1959-01-06 Nat Distillers Chem Corp Preparation of dialkoxy alkyl derivatives of dimers of conjugated olefins
US2816914A (en) * 1956-05-09 1957-12-17 Nat Distillers Chem Corp Dimerization process
DE1192640B (de) * 1961-12-05 1965-05-13 Basf Ag Verfahren zur Herstellung von Mischoligomeren aus 1, 3-Dienen und Acrylsaeureestern,Acrylsaeureamid oder Acrylsaeurenitril
DE2908928A1 (de) * 1979-03-07 1980-09-18 Studiengesellschaft Kohle Mbh Verfahren zur herstellung von organolithiumverbindungen neben lithiumhydrid

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US2019832A (en) * 1933-09-29 1935-11-05 Du Pont Reactions of sodium with hydrocarbons
US2171868A (en) * 1936-04-09 1939-09-05 Du Pont Alkali metal derivatives of acetylenic hydrocarbons
US2352461A (en) * 1942-02-25 1944-06-27 Du Pont High molecular weight unsaturated organic acids and process of preparing them
US2773092A (en) * 1954-12-06 1956-12-04 Ethyl Corp Dimerization process

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GB190023727A (en) * 1900-12-28 1901-12-21 Charles Moureu Manufacture of Useful Products from Heptine and Octine.
US2019832A (en) * 1933-09-29 1935-11-05 Du Pont Reactions of sodium with hydrocarbons
US2171868A (en) * 1936-04-09 1939-09-05 Du Pont Alkali metal derivatives of acetylenic hydrocarbons
US2352461A (en) * 1942-02-25 1944-06-27 Du Pont High molecular weight unsaturated organic acids and process of preparing them
US2773092A (en) * 1954-12-06 1956-12-04 Ethyl Corp Dimerization process

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3013071A (en) * 1957-12-02 1961-12-12 Nat Distillers Chem Corp Diolefin dimers and acid derivatives thereof
US2956087A (en) * 1958-12-04 1960-10-11 Nat Distillers Chem Corp Dimerization of vinyl aromatic compounds
US3012986A (en) * 1959-07-09 1961-12-12 Nat Distillers Chem Corp Urea-formaldehyde modification of branched chain polyamides and product obtained thereby
US3061582A (en) * 1959-07-09 1962-10-30 Nat Distillers Chem Corp Ethylenic modification of branched chain polyamides
US3061581A (en) * 1959-07-09 1962-10-30 Nat Distillers Chem Corp Vinyl modification of branched chain polyamides
US3243287A (en) * 1962-09-14 1966-03-29 Crucible Steel Co America Hot strength iron base alloys
US4034000A (en) * 1963-09-23 1977-07-05 The Goodyear Tire & Rubber Company Difunctional polymeric dienes
US3686299A (en) * 1968-01-31 1972-08-22 Montedison Spa Process for the preparation of acyclic dicarboxylic acids from dienic hydrocarbons
US3716594A (en) * 1969-04-01 1973-02-13 Nippon Soda Co Process for the production of living oligomer

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Publication number Publication date
CH322988A (fr) 1957-07-15
CH327718A (fr) 1958-02-15
DE1150679B (de) 1963-06-27
FR1093096A (fr) 1955-04-29
CH331850A (fr) 1958-08-15

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