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US2923718A - Fatty acid condensation products and process of preparation - Google Patents

Fatty acid condensation products and process of preparation Download PDF

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Publication number
US2923718A
US2923718A US549173A US54917355A US2923718A US 2923718 A US2923718 A US 2923718A US 549173 A US549173 A US 549173A US 54917355 A US54917355 A US 54917355A US 2923718 A US2923718 A US 2923718A
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Prior art keywords
acid
reaction
fatty acids
heating
residue
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Mikusch-Buchberg Johannes Von
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Lever Brothers Co
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Lever Brothers Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S106/00—Compositions: coating or plastic
    • Y10S106/901—Low molecular weight hydrocarbon polymer-containing mixture

Definitions

  • This invention relates to novel-condensation products, more particularly to condensation products obtained by the treatment of fatty acids which are useful in industrial compositions.
  • the starting materials are unsaturated the resulting products are particularly useful as drying compositions in paints, varnishes, core oils, linoleum and similar products for partly or wholly replacing drying oils.
  • the resulting products are useful, for example, as quenching oils or plasticizers.
  • novel fatty condensation products are obtained by heating non-hydroxylated fatty acids or mixtures containing a substantial amount of nonhydroxylated fatty acids, in the presence of a small amount of a catalyst, to a temperature between 220 and 330 C., with removal of the water formed in the reaction until the product contains a substantial amount of unsaponifiable matter having a mean molecular weight in accordance with that calculated for a condensation product of at least three molecules of fatty acid. Temperatures of between 250 and 300 C. are preferred.
  • Heating should be carried out under vacuum.
  • the reaction temperature may not at once attain the range 220-330 C. since the mixture in the first stage of the reaction may boil at a lower temperature than 220 C., fatty acids passing into the vapour phase together with volatile reaction products. As the reaction proceeds the concentration of fatty acids.in the mixture is reducedv and the boiling point of the mixture increases, so that the temperature can gradually be raised.
  • heating is preferably carried out while refluxing the fatty acids and higher boiling compounds. In this way a greater part of the starting material may be converted into the final condensation product.
  • the starting material may contain other constituents such as, for example, mono-, dior tri-glycerides, or resin acids.
  • the mixture should contain a substantial or, preferably, a major amount of fatty acids.
  • Such other constituents have a tendency to slow down the desired reaction and too great a proportion should be avoided. Even when they possess sufficient drying properties by themselves or develop them on heating, the amount of additional constituents should not exceed the amount of fatty acids by weight.
  • Fatty acids for use according to the invention should preferably have the formula where R is a hydrocarbon group, preferably a :long saturated hydrocarbon chain, which is preferably unsubstituted.
  • the fatty acids must not contain hydroxyl groups in the hydrocarbon chain. It is preferred that R is an unsaturated alkyl group, preferably of a chain length of from 9 to 25 carbon atoms, most preferably of a chain length of from 17 to 21 carbon atoms.
  • fatty acids which have a relatively low iodine value heating can be carried out at high temperatures for a long time, and highv proportions of unsaponifiable matter, e.g. to nearly can be obtained.
  • heating may have to be discontinued earlier, since gelation may take place and the proportion of unsaponifiable matter may then be lower, e.g. 40-60%.
  • the fatty acids used as starting materials may in some cases with advantage be purified according to the usual methods.
  • the catalystused in the processes of the invention may be an oxygen-containing boron compound.
  • Preferred inorganic boron compounds are boric acid and alkali pentaborates, preferably ammonium pentaborate, may also be used with advantage.
  • Borax however, has only a slight activity as a catalyst. with oxidizing properties are not preferred.
  • the amount of catalyst may vary widely, for example, between 0.1 and 10% by weight of the starting material. An amount of catalyst of from 26%, by weight is in general preferred.
  • the process is preferably carried out in a stainless steel reaction vessel provided with a reflux column.
  • the latter may be either heated or cooled, so as to reflux the fatty acids and other higher boiling products and to distil otf reaction water and other volatile products and gases.
  • the water and other volatile products may be condensed in a cooled trap together with any entrained higher boiling products.
  • the catalyst may be mixed with the starting material or added during the heating in the reaction vessel, or it can be placed in the column.
  • the reflux column may be packed, for example, with helices, Raschig rings or the like.
  • the reflux column may also be regulated in such a way that part of'the fatty acids is alowed to distill ofi. 7
  • Boron compounds mixture may be extracted with a suitable solvent, for example alcohol.
  • the reaction mixture may be distilled under vacuum to remove unchanged fatty acid.
  • the residue after solvent treatment or distillation is the desired product.
  • the reaction mixture is filtered, washed with hot water to remove the catalyst and dried under vacuum before or after solvent treatment or distillation.
  • the distillate or the alcohol extract obtained according to the processes of the invention may be re-used for a further reaction since it consists substantially of unchanged starting material. it the reaction is allowed to proceed to a stage where only a small proportion of unchanged starting material is contained in the reaction mixture there may be no need to remove these starting materials.
  • the condensation products of the invention are characterised by a substantial amount, preferably at least 40%, of unsaponifiable matter, a low acid and saponification value, an increased iodine value according to Wijs as compared to the starting material, and a high mean molecular weight.
  • the mean molecular weight of the unsaponifiable portion is roughly in accordance with, or higher than, the calculated molecular weight of a theoretical condensation product of three molecules of fatty acid.
  • the condensation products have drying properties when the iodine value (determined according to Wijs method) is 100 or higher.
  • the condensation products have a molecular structure which contains at least three alkyl chains. Preferred products are those in which the alkyl chains are those of unsaturated acids derived from fatty oils.
  • the invention also includes the use of the above mentioned products having an iodine value (determined by Wijs method) of 100 or higher, to replace drying materials, such as drying oils, oleo resinous varnishes or alkyd resins in the paint, varnish, linoleum and allied industries.
  • drying materials such as drying oils, oleo resinous varnishes or alkyd resins in the paint, varnish, linoleum and allied industries.
  • the new products may be mixed with the usual siccatives based on cobalt, lead or manganese and may be diluted with turpentine, mineral spirits and/ or other volatile solvents to the desired viscosity.
  • temperatures quoted are those of the metal bath surrounding the reaction vessel.
  • the temperature within the reaction mixture was lower, by about 20 and 30 C. during the initial stages and by about 10 C. during the final stages of the reaction.
  • Example 1 grams fatty acids obtained from Norwegian herring oil by the Twitchell process (acid number of the herring oil acids: 182.7; iodine value: 132.7) and 2.75 grams crystalline boric acid were introduced into a 250 ccs. flask above which a fractionating column was vertically mounted. The column was connected to a vacuum pump through an air-cooled condenser mounted parallel to the fractionating column and a reception flask was provided at the bottom of the condenser. The fractionating column was provided with a packing consisting of stainless steel helices or glass Raschig rings.
  • the flask was slowly heated in a metal bath until the bath temperature was 290 C. The heating was carried out for 60 minutes until the bath temperature was 210 C. Heating was further continued for a further minutes to raise the bath temperature from 210 to 290 C. The bath was maintained at 290 C. for 3 hours.
  • the fractionating column was heated to about C. by electrical resistance heating. At bath temperatures of from about 210 C. upwards some material commenced to distill olf into the receiving fiask. Condensation of material passing into the fractionating column commenced at a lower bath temperature. After the heating had been continued for 3 hours at 290 C. the reaction mixture was allowed to cool.
  • Example 2 110 grams herring oil fatty acids (acid number: 182, iodine value: 142.7) and 6.6 grams of ammonium pentaborate were heated in the apparatus of Example 1 for 60 minutes to a bath temperature of 210 C., then in 150 minutes to a bath temperature of 290 C. and finally for 60 minutes at a bath temperature of 290 C. After cooling 55.5 grams of residue which had the consistency of a highly viscous stand-oil was present in the reaction vessel.
  • Example 3 Commercial distilled linseed fatty acids (iodine number: 165) were slowly heated in the apparatus of Example 1 together with 6% by weight of boric acid until the bath temperature was up to 290 C. The heating was continued until about 25% of the original material distilled off as water (about 7%) and fatty acids (about 18%). The residue after the addition of siccatives and thinning dried in 3 /2 hours to a practically non-tacky and colourless film and was suitable for replacing boiled linseed oil in the preparation of paints or for use as a clear varnish.
  • siccatives and thinning dried in 3 /2 hours to a practically non-tacky and colourless film and was suitable for replacing boiled linseed oil in the preparation of paints or for use as a clear varnish.
  • the product showed a remarkable increase in iodine number.
  • the concentrate before heating had an iodine number of 180 according to both the Wijs method and were treated in a round-bottom flask.
  • the fractiona-' saponifiable part of the product (73.4%) showed a still higher iodine number, viz. 224 according to the Wijs method and 250 according to the Woburn method and a diene number according to the Ellis-J ones method of 10.3.
  • the unsaponifiable portion of the residue obtained by solvent extraction after saponification had still better drying properties than the product as a whole, drying after addition of siccatives and on thinning to a very hard film equalling china wood oil in hardness and with good water and alkali resistance.
  • the fatty distillate which had collected in the receiver and amounted to about 22% by weight of the material consisted largely of unchanged although contaminated linoleic acid and could be used again. It had an acid number of 143.0, a saponification number of 190.6 and an iodine number of 1708. About 6% ofwater had collected in a chilled trap in the vacuum'line.
  • Example 5 110 grams of cottonseedfatty acids obtained by the commercial distillation of the cotton-soapstock fatty acids tion column was mounted thereon and provided with the packing as described in Example 1. It also contained 6.6 grams of boric acid in the form of pieces obtained by applying a high pressure to a slurry of finely pulverized crystalline boric acid and a small amount of water in a tablet press and afterwards drying at about 70 C. in an oven. After evacuation of the apparatus the reaction vessel was heated as in Example 2. A residue of 47 grams remained, which after the addition of thinner and 'driers dried in 3 /2 hours and yielded a hard, elastic and non-tacky film of good surface coating properties.
  • Example 5 grams of boric acid, which had been distributed in the reflux column as in Example 5. The times and temperatures were as described in Example 2. In addition to 6.4 grams of a fatty acid-distillate with an iodine number of 52, consisting mainly of a mixture of oleic and palmitic acids, 7.7 grams of an aqueous distillate were collected. The bulk of the material which remained in the flask was washed with hot water to remove dissolved boron compounds.
  • the residue After being thus purified, the residue had a refractive index of 1.4776, an acid number of 58.1, a saponification number of 85.6, an iodine value of 132.9, and a mean molecular weight of 661 as opposed to the values for the oleic acid which were refractive index: 1.4580, acid number: 198.5, saponification number: 199.3 and iodine number 88.0.
  • the oleic acid had been free of unsaponifiable matter, the residue contained 44.7% unsaponifiable matter.
  • the residue was soluble in ether and petroleum spirit but insoluble in alcohol and acetic acid. There was an overall weight loss of about 2 /2 of the starting material due to gaseous decomposition products.
  • Example 7 110 grams of groundnut oil fatty acids (acid number: 197.6; iodine number 98.7) were heated under vacuum in a flask fitted with a column containing Raschig rings was raised to 290 C. and held at this temperature for 1 hour. Owing to the use of the reflux condenser, there was no distillate other than an aqueous fraction of about 8 grams which was condensed in a chilled trap in the vacuum line. The yield of residue was about including the samples which had been taken from time to time to 'follow the rise in iodine number and the drop in acid value caused by the increase in unsaponifiable content. The iodine value of the residue at the end of the experiment was 123.8, its acid value 70.6.
  • Example 8 A mixture of neutral oil and free fatty acids obtained during alkali-refining of rapeseed oil with an acid number of 112 and iodine number of 126.8 was treated with 6% of boric acid in the apparatus and manner described in Example 2. The residue, 77% by weight of the original fatty compound, was a viscous oil with an iodine value of 146.1. After addition of thinner and metal driers a film after drying for 19 hours exhibited only a slight tackiness.
  • Example 9 20 kilograms of refined sunflower soapstock fatty acids having an acid value of 160, a saponification value of 196, and an iodine value of 127, together with 0.5 kilogram of technically pure boric acid were heated under a vacuum of 15 to 25 nuns. mercury in a stainless steel apparatus such as is used in manufacturing stand oil and alkyd resins.
  • This apparatus consisted of a gas-heated 50 litre boiler including a stirring device and a vacuum sample taker and a reflux cooler mounted on the boiler and connected to a tubular cooler slanting towards the receiver. The heating was carried out over 3 hours until the temperature was raised to 260 C., continued for a further 4 /2 hours to raise the temperature to 290 C., and then for a further 4 hours at 290 C. During this time 5.5 kilograms of fatty acid and 0.8 kilogram of water collected in the receiver.
  • Example 10 In the apparatus described in Example 9, 20 kilograms of a fraction obtained from soya bean oil fatty acids (acid value 203.5, saponification value 206.3, iodine value according to Wijs 140.2, unsaponifiable matter 2.8%) and 0.4 kilogram technical boric acid were heated under a vacuum of 13-20 mrn. to 260 C. within 10 hours and to 290 C. in 2 further hours. The fatty acids distilled off during this heating were continuously fed back to the reaction kettle. Then the heating was continued for 4 hours at a temperature between 260 and 290 (3., during which time, however, the distillate obtained was collected in the receiver.
  • Example 11 20 kilograms distilled tall oil fatty acids with acid value 194.3, sapo'nification value 196.9, iodine value according to Wijs 131.5, resin content 2%, and 0.4 kilogram technical grade boric acid are heated, with mechanical stirring, over two hours to 230 C. in the apparatus described in Example 10 under a vacuum of 412 mm. mercury. Heating was then carried out for a further 10 hours to 260 C. and then carried out for 14 hours in the range 260 to 290 C. The fatty acids distilling on were reintroduced into the kettle. Towards the end of the reaction only slight amounts of fatty acids were distilling otf. After completion of the heating 17.5 kilograms of residue were obtained and washed five times, with 20 kilograms hot water each time, until the boric acid had been removed. The residue was then dried in vacuum and filtered in a filter press. The product thus obtained showed the following characteristics:
  • a process for preparing condensation products which comprises heating an acid of the formula R.C0.0H where R is an unsubstituted long chain hydrocarbon radical, at a temperature of 220 to 330 C. in the presence of a catalyst selected from the group consisting of boric acid, boric oxide, ammonium pentaborate, trimethyl borate, triethyl borate, mannitol borate and the mixed anhydrides of boric acid and fatty acid, until the reaction mixture contains at least 32% by weight of unsaponifiable matter having a mean molecular weight at least three times that of said acid, the heating being carried out under such conditions that water liberated during the reaction is removed from the reaction zone as it is formed but the loss of the major part of the acid is avoided.
  • a catalyst selected from the group consisting of boric acid, boric oxide, ammonium pentaborate, trimethyl borate, triethyl borate, mannitol borate and the mixed anhydrides of boric acid and fatty acid
  • a process for preparing condensation products which comprises heating an acid of the formula R.C0.0H where R is an unsubstituted long chain hydrocarbon radical, at a temperature of 220 to 330 C. in the presence of a catalyst selected from the group consisting of boric acid, boric oxide, ammonium pentaborate, trimethyl borate, triethyl borate, mannitol borate and the mixed anhydrides of boric acid and fatty acid, until the reaction mixture contains at least 32% by weight of unsaponifiable matter having a mean molecular weight at least three times that of said acid, the heating being carried out under such conditions that water liberated during the reaction is removed from the reaction zone as it is formed but the loss of the major part of the acid is avoided,
  • reaction mixture being kept at 250 to 300 C. at least during the latter part of the reaction.
  • a process for preparing condensation products which comprises heating an acid of the formula R.C0.0H where R is an unsubstituted long chain hydrocarbon radical, at a temperature of 220 to 330 C. in the presence of a boric acid catalyst, until the reaction mixture contains at least 32% by weight of unsaponifiable matter having a mean molecular weight at least three times that of said acid, the heating being carried out under such conditions that water liberated during the reaction is removed from the reaction zone as it is formed but the loss of the major part of the acid is avoided.
  • a process for preparing condensationproducts whichcomprises heating an acid of the formula R.C0.0H where v R is an unsubstituted long chain hydrocarbon radical, at a temperature of 220 to 330 C. in the presence of a boric oxide catalyst, until the reaction mixture contains at least 32% by weight of unsaponifiable matter having a mean molecular weight at least three times that of said acid, the heating being carried out under such conditions that water liberated during the reaction is removed from the reaction zone as it is formed but the loss of the major part of the acid is avoided.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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US549173A 1954-11-30 1955-11-25 Fatty acid condensation products and process of preparation Expired - Lifetime US2923718A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3404064A (en) * 1963-08-01 1968-10-01 Allied Chem Method of sizing paper with fatty acid condensation products
US5387705A (en) * 1993-08-13 1995-02-07 The Procter & Gamble Company Fatty acid anhydride process

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1987559A (en) * 1931-12-23 1935-01-08 Firm Henkel & Cie Gmbh Process of producing boron tricarboxylates
US1988021A (en) * 1931-08-08 1935-01-15 Ig Farbenindustrie Ag Production of unsaturated ketones
GB470498A (en) * 1935-12-14 1937-08-16 Ind Mij Nv Deventer Improvements in and relating to the treatment of drying oils, semi-drying oils, corresponding fatty acids, and products derived therefrom
US2308184A (en) * 1937-12-07 1943-01-12 Standard Oil Dev Co Art of producing wax modifying agents
US2395012A (en) * 1943-05-18 1946-02-19 Carbide & Carbon Chem Corp Production of ketones
US2465337A (en) * 1944-11-01 1949-03-29 Du Pont Process of preparing ketenes
US2482761A (en) * 1946-07-06 1949-09-27 Emery Industries Inc Polymerization of unsaturated fatty acids
US2513825A (en) * 1946-04-10 1950-07-04 Du Pont Preparation of ketenes
US2544365A (en) * 1946-04-10 1951-03-06 Du Pont Acylated phenol-formaldehyde resins containing ketene polymers of higher fatty acids
US2729658A (en) * 1951-12-17 1956-01-03 Clarence B Croston Polymerization process using boron fluoride
US2781386A (en) * 1950-09-09 1957-02-12 Willy Spangenberg & Co Manufacturing drying paints

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1988021A (en) * 1931-08-08 1935-01-15 Ig Farbenindustrie Ag Production of unsaturated ketones
US1987559A (en) * 1931-12-23 1935-01-08 Firm Henkel & Cie Gmbh Process of producing boron tricarboxylates
GB470498A (en) * 1935-12-14 1937-08-16 Ind Mij Nv Deventer Improvements in and relating to the treatment of drying oils, semi-drying oils, corresponding fatty acids, and products derived therefrom
US2308184A (en) * 1937-12-07 1943-01-12 Standard Oil Dev Co Art of producing wax modifying agents
US2395012A (en) * 1943-05-18 1946-02-19 Carbide & Carbon Chem Corp Production of ketones
US2465337A (en) * 1944-11-01 1949-03-29 Du Pont Process of preparing ketenes
US2513825A (en) * 1946-04-10 1950-07-04 Du Pont Preparation of ketenes
US2544365A (en) * 1946-04-10 1951-03-06 Du Pont Acylated phenol-formaldehyde resins containing ketene polymers of higher fatty acids
US2482761A (en) * 1946-07-06 1949-09-27 Emery Industries Inc Polymerization of unsaturated fatty acids
US2781386A (en) * 1950-09-09 1957-02-12 Willy Spangenberg & Co Manufacturing drying paints
US2729658A (en) * 1951-12-17 1956-01-03 Clarence B Croston Polymerization process using boron fluoride

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3404064A (en) * 1963-08-01 1968-10-01 Allied Chem Method of sizing paper with fatty acid condensation products
US5387705A (en) * 1993-08-13 1995-02-07 The Procter & Gamble Company Fatty acid anhydride process

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