US3441577A - Process for the co-oligomerization of conjugated unsaturated fatty acids or their esters with indene and/or coumarone - Google Patents

Process for the co-oligomerization of conjugated unsaturated fatty acids or their esters with indene and/or coumarone Download PDF

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Publication number
US3441577A
US3441577A US441874A US3441577DA US3441577A US 3441577 A US3441577 A US 3441577A US 441874 A US441874 A US 441874A US 3441577D A US3441577D A US 3441577DA US 3441577 A US3441577 A US 3441577A
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US
United States
Prior art keywords
indene
coumarone
fatty acids
unsaturated fatty
acid
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US441874A
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English (en)
Inventor
Josef Baltes
Friedrich Weghorst
Otto Wechmann
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Harburger Fettchemie Brinckman and Mergell GmbH
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Harburger Fettchemie Brinckman and Mergell GmbH
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • 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
    • C08F244/00—Coumarone-indene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
    • C08G18/4233—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups derived from polymerised higher fatty acids or alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/137—Acids or hydroxy compounds containing cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
    • C09F7/00—Chemical modification of drying oils

Definitions

  • the present invention relates to a process for cationic co-oligomerization of conjugated-unsaturated fatty acids or their esters with indene and/or coumarone.
  • beta-eleostearic acid yields l-(n-hexen-l-yl)-4-(carbmethoxy-n-heptyl) 1,4,10,11 tetrahydrofluorene
  • 9,12- linolic acid yields 1 n heXyl-4-(carbmethoxy-n-heptyl)- 1,4,10,1l-tetrahydrofluorene.
  • indene functions as a dienophilic reactant.
  • 9,12- linolic acid the acid is converted first to the corresponding conjudiene fatty acid, which is then subjected to the diene synthesis with indene.
  • conjugated-unsaturated fatty acids or their esters or fatty acids or ester mixtures containing conjugated-unsaturated fatty acids can be cooligomerized with indene and/or coumarone by cationic reaction.
  • the process of the invention comprises reacting in the presence of an acid catalyst or catalysts of the Friedel-Crafts type one mol of the conjugated, unsaturated fatty acids or esters of the acids with from 0.5 to 20 mols of indene and/or coumarone. To prevent the formation of any free radicals which otherwise might affect the result, the reaction is conducted in the presence of a phenolic inhibitor.
  • isomerized monoesters of half-drying oils such as isomerized soya oil fatty acid methyl ester, isomerized safilower oil fatty acid methyl ester and the like containing 40 to of conjugated-unsaturated fatty acid in ester bond and indeneand/or coumarone-containing hydrocarbon mixtures such as the coal tar oil fractions designated as Losungsbenzol II or solvent naphtha are used.
  • the isomerized fatty acid monoesters used as starting material are obtained from isolated-unsaturated fatty acid monoesters according to our United States Patent No. 3,162,658, Dec. 22, 1964, to which reference is made.
  • the fatty acid ester is an ester of a hydrocarbyl alcohol having 1 to 18 carbon atoms.
  • the fatty acid monoesters are mixed with indene and/or coumarone or the corresponding amounts of Losungsbenzol II in a ratio of 0.5 to 20 mols of indene and/or coumarone per mol of conjugated-unsaturated fatty acid or its monoester and heated in the presence of acid catalysts, e.g., acid activated bleaching earth, with stirring and gradual temperature increase until in the temperature range between 40 and C. the co-oligomerization commences. This stage is indicated by the spontaneous temperature increase of the reaction mixture. For completion of the reaction, the mixture is heated-if necessary with a temperature increase up to a maximum of C. When using Losungsbenzol II, however, the temperature limit is its boiling point. Heating is continued under reflux until there is no change in the viscosity of the reaction mixture.
  • acid catalysts e.g., acid activated bleaching earth
  • the conversion is carried out in the presence of small amounts of phenolic inhibitors such as hydroquinone, butyl catechol and the like. In general, the reaction requires 1 to 4 hours.
  • the fatty acids which do not participate in the reaction namely saturated and monounsaturated fatty acids, are removed by distillation under reduced pressure.
  • Losungsbenzol II the reacted hydrocarbons derived from Losungsbenzol II, mainly higher benzene homologues, are removed in the same manner.
  • the residues are liquid to highly viscous to solid resinous homogeneous masses, which comprise in large part polybasic carboxylic acids together with monocarboxylic acids and are characterized by their acid number or saponification number.
  • the products obtained with a low molar ratio of the reaction components can be distilled without decomposition under high vacuum.
  • the process of the invention is applicable only to conjugated-unsaturated fatty acids and their esters: not to isolated-unsaturated fatty acids and their esters. Under the conditions of the process, a homo-oligomerization of the single reactants is practically excluded. This is shown by the very small amounts of unsaponifiable components present in the products obtained by the process of the invention.
  • This, and the acid catalysts or Friedel-Crafts catalysts which are used as well as the necessity to exclude peroxides which could act as catalysts in the sense of a free-radical reaction characterize the process as a cationic co-oligomerization.
  • the products obtained by the process of the invention are mixtures of isomeric monoand polycarboxylic acids or their esters. Typical examples of such acids, starting, e.g., from 9,11-
  • n integer.
  • the new products obtained by the process of the invention differ substantially from the known diene adducts as well as from the addition products formed by radicalic reactions, which are all monocarboxylic acids.
  • the main advantage of the present invention is that it permits the addition of about 15 to 700 parts by weight of indene and/or coumarone to 100 parts by weight of conjugated-unsaturated fatty acids or their esters to form chemically defined monoand polycarboxylic acids or their esters which due to their favorable properties are useful for a great variety of applications.
  • the products obtained by the process of the invention exhibit an outstanding light stability. Therefore, they are especially suitable for the manufacture of nonyellowing lacquers and coatings, the chemical and mechanical properties of which can be widely varied and adapted to the desired properties by selection of the molar ratio of indene/conjugated-unsaturated fatty acids.
  • a further advantage of the invention is that a ratio of 0.5 to about 2 mols indene and/or coumarone per mol conjugated-unsaturated fatty acid, oligomeric dicarboxylic acids are obtained as a main product which due to their bifunctional character are accessible to polyaddition or polycondensation and can be used therefore for the manufacture of plastics, e.g., polyarnides.
  • plastics e.g., polyarnides.
  • plastics e.g., polyarnides.
  • EXAMPLE 1 600 g. of isomerized sunflower oil fatty acid methyl ester containing 65% conjugated-unsaturated fatty acid methyl ester (about 1.3 mols), 116 g. of indene (1 mol), 6 g. of acid activated bleaching earth and 0.5 g. of hydroquinone were heated with stirring in an atmosphere of nitrogen; the indene was dissolved within a short time. After the mixture had reached a temperature of about C., a brownish discoloration of the catalyst was observed. At the same time, the temperature spontaneously increased to C. within a few minutes. The reaction mixture was maintained at 140 C.
  • distillate corresponding to 34.2% was obtained showing a saponifi cation number of 185 and containing 1.2% of unsaponifiable matter.
  • the distillation residue weighing 470 g. corresponding to 65.8% had a saponification number of 146 and contained 2.2% of unsaponifiable.
  • the free total fatty acids recovered from a part of this residue had a saponification number of 156.
  • 100 g. of the distillation residue were subjected to fractional distillation at 0.1 torr. The boiling ranges and characteristics of the single fractions are shown in the following table:
  • Example 2 All other working conditions were the same as used in Example 1 with the exception that, when distilling the co-oligomerisate, the hydrocarbons and fatty acid methyl esters were recovered in separate fractions.
  • the following table shows typical batches lected from the class consisting of hydroquinone, butyl catechol, and di-tertiary-butyl-para-cresol.
  • Process for the cationic co-oligomerization of conjugated, unsaturated fatty acids with a compound selected from the class consisting of indene, coumarone, and mixtures thereof which comprises reacting a substance selected from the class consisting of conjugated, unsatlrated fatty acids and esters of such acids with hydrocarbyl alcohols having 1 to 18 carbon atoms in the proportions of 1 mol of said acid substance to from 0.5 to 20 mols of the said indene and/or coumarone compound, conducting the reaction at temperatures from 40 to 180 C.
  • a catalyst selected from the group consisting of acid and Friedel-Crafts catalysts, and a phenolic inhibitor of free-radical reaction, for a time suflicient to bring about a stable, increased viscosity in the reaction mass.
  • a process according to claim 5 wherein said substance is a member of the group consisting of the methyl ester of isomerized soya oil fatty acids, isomerized safliower oil fatty acids and isomerized sunflower oil fatty acids.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US441874A 1964-08-22 1965-03-22 Process for the co-oligomerization of conjugated unsaturated fatty acids or their esters with indene and/or coumarone Expired - Lifetime US3441577A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEH0053613 1964-08-22

Publications (1)

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US3441577A true US3441577A (en) 1969-04-29

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Country Status (7)

Country Link
US (1) US3441577A (xx)
AT (1) AT250941B (xx)
BE (1) BE660017A (xx)
CH (1) CH438275A (xx)
GB (1) GB1040037A (xx)
NL (2) NL6502656A (xx)
SE (1) SE325022B (xx)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4508652A (en) * 1981-06-25 1985-04-02 National Distillers And Chemical Corporation Process for the trimerization of unsaturated fatty acids
CN105693930A (zh) * 2014-11-25 2016-06-22 上海宝钢化工有限公司 一种羧基古马隆树脂及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1007914B (de) * 1953-03-30 1957-05-09 Gelsenkirchener Bergwerks Ag Verfahren zur Herstellung von Lackbindemitteln
GB950602A (en) * 1959-05-29 1964-02-26 Centre Nat Rech Scient Improvements relating to polymers and copolymers of indene and processes for their preparation
US3271432A (en) * 1962-04-25 1966-09-06 Brinckmann Harburger Fett Process for the manufacture of polybasic araliphatic carboxylic acids and products thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1007914B (de) * 1953-03-30 1957-05-09 Gelsenkirchener Bergwerks Ag Verfahren zur Herstellung von Lackbindemitteln
GB950602A (en) * 1959-05-29 1964-02-26 Centre Nat Rech Scient Improvements relating to polymers and copolymers of indene and processes for their preparation
US3271432A (en) * 1962-04-25 1966-09-06 Brinckmann Harburger Fett Process for the manufacture of polybasic araliphatic carboxylic acids and products thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4508652A (en) * 1981-06-25 1985-04-02 National Distillers And Chemical Corporation Process for the trimerization of unsaturated fatty acids
CN105693930A (zh) * 2014-11-25 2016-06-22 上海宝钢化工有限公司 一种羧基古马隆树脂及其制备方法

Also Published As

Publication number Publication date
NL6502656A (xx) 1966-02-23
GB1040037A (en) 1966-08-24
SE325022B (xx) 1970-06-22
AT250941B (de) 1966-12-12
NL123922C (xx)
BE660017A (xx) 1965-06-16
CH438275A (de) 1967-06-30

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