US2793220A - Method of making polymeric acids - Google Patents

Method of making polymeric acids Download PDF

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Publication number
US2793220A
US2793220A US475006A US47500654A US2793220A US 2793220 A US2793220 A US 2793220A US 475006 A US475006 A US 475006A US 47500654 A US47500654 A US 47500654A US 2793220 A US2793220 A US 2793220A
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US
United States
Prior art keywords
fatty acids
acids
equivalent
reaction
polyunsaturated fatty
Prior art date
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
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US475006A
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English (en)
Inventor
Fred O Barrett
Charles G Goebel
Robert M Peters
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Emery Oleochemicals LLC
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Emery Oleochemicals LLC
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Priority to BE543587D priority Critical patent/BE543587A/xx
Priority to NL92418D priority patent/NL92418C/xx
Application filed by Emery Oleochemicals LLC filed Critical Emery Oleochemicals LLC
Priority to US475006A priority patent/US2793220A/en
Priority to GB33239/55A priority patent/GB825534A/en
Priority to DEE11672A priority patent/DE1134666B/de
Priority to FR1152544D priority patent/FR1152544A/fr
Application granted granted Critical
Publication of US2793220A publication Critical patent/US2793220A/en
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    • 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
    • C09F7/06—Chemical modification of drying oils by polymerisation
    • 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
    • C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
    • C08F20/64—Acids; Metal salts or ammonium salts thereof

Definitions

  • This invention relates to a process of manufacturing polycarboxylic fatty acids of high purity and light color Which are suitable for use in the resin industry as components of alkyd and polyamide resins. These polymeric fatty acids may also be used for many other purposes such as the manufacture of aluminum lubricating greases, and reducing the corrosiveness of gasoline.
  • polyunsaturated fatty acids such as linblenic acid, linoleic acid and their higher molecular weight homologues recovered from marine oils and the alkyl esters of these fatty acids polymerize by reaction of double bonds to form polyfunctional polymers.
  • the technical literature including the issued patents, has advocated the polymerization of the alkyl esters of the polyunsaturated fatty acids such as methyl linoleate, as distinguished from linoleic acid, because of the degradation and impairment of color which normally attends the attempt to polymerize the acids as such.
  • polymerization of the alkyl esters has been considered desirable because of superior yields of polymer both quantity-wise and quality-wise.
  • the prior literature has also advocated the use of catalysts, such as fullers earth or bentonite, preferably acid treated, or stannic chloride, to permit the use of lower temperatures and/ or shorter periods of time in the thermal process.
  • catalysts such as fullers earth or bentonite, preferably acid treated, or stannic chloride
  • the object of the present invention is to provide a The present invention is based upon the discovery and determination that acid activated clays do not act to catalyze the production of thermal dimers, but rather, when properly employed as hereinafter described, they bring about the formation of an entirely different type of polymeric acid by an entirely different mechanism.
  • the content of free acids may be-determined by titration with a standard alkali and the grams of acidic material required to react with one equivalent weight of alkali may be termed the neutralization equivalent. If the fatty material is heated with an excess of alkali and the amount of both the free and the combined carboxylic acids is determined, then the grams of material required to react with one equivalent of alkali may be termed the saponification equivalent.
  • esters of the acids are used instead of the free acids, these changes are not only obscured by the absence of free acid groups by which the course of the reaction may be followed, but in addition, the esters appear to be incapable of transesterifying to form the intermediate inter ester the formation of which seems to be a necessary preliminary step to the formation of polymeric'acids. As a result, the yields of polymeric acids are much lower when esters are employed, and what yield is obtained seems to be the result of a certain amount of unavoidable hydrolysis of the ester.
  • the process of our invention does not consist of merely carrying out a thermal polymerization at a lower temperature made possible by a clay catalyst but, rather, consists of a method of treating polyunsaturated acids with active clays and water to bring about first the formation of an inter ester and then the decomposition of the inter ester to form polymeric acids. These reactions are not consecutive in that one is entirely completed before the other begins but, rather, are occurring simultaneously and concurrently with the formation of inter ester predominating at the beginning of the treatment and the conversion to polymeric acids predominating at the end of the treatment.
  • the ditference in method of formation of the polymeric acids by the process of our invention when compared to the direct ring formation postulated for the thermal method would indicate a difierence in structural formula of the final products.
  • An examination of the products produced by the two methods shows that the iodine value of the polymeric acids produced by our process is from 20-30 points higher than thermal polymeric acids produced from the same raw material.
  • the polymeric acids from soya fatty acids have an iodine value of 90-95 when produced by the thermal method but an iodine value of 126 when produced by the method of this invention.
  • the iodine values may not be a true measure of the number of double bonds present, but at least they are indicative of differences in the structures of the two products.
  • the process of our invention therefore, consists of heating the mixed fatty acids derived from oils or fats whose unsaturated acid content consists predominately of polyunsaturated acids with small amounts of crystalline clay mineral and small amounts of water until the neutralization equivalent of the polymerized portion approaches within 25 points, and preferably 10-15 points, of the saponification equivalent.
  • the temperature of heating may range from 180 to 260 C., with the preferred temperature being from 215 to 240 C.
  • the time of treatment is to a degree reversely proportional to the temperature and may range from as high as 8 hours at the lower temperatures to as low as 2 hours at the higher temperature and 3 to 4 hours at the preferred temperature.
  • the amount of clay employed is not particularly critical except that in the case of low quality acids, a quantity in excess of the minimum required may be needed to absorb color or other impurities.
  • the amount may, therefore, range from 1% to as high a quantity as is economically sound practice, or 20% of the weight of the acids being treated.
  • clay minerals such as: montmorillonite, kaolinite, hectorite, halloysite, attapulgite, sepialite.
  • clays vary considerably in composition, depending upon the locality of thedeposit and other factors, and many of the commercial clays are mixtures of different chemical compounds.
  • the commercial bentonites may be used in the practice of this process if they contain suflicient montmorillonite, say 75%.
  • Commercial clays having lesser percentages of crystalline clay mineral may be employed, but it is the crystalline clay minerals which promote the reaction.
  • clay minerals While there may be rare crystalline clay minerals-which cannot be used in this process, such clay minerals are not commercial products and are not mined for the market. All of the mined commercial crystalline clay minerals may be used in this process with good results.
  • the bentonitic clays containing at least 75% montmorillonite are particularly recommended.
  • the pH of the clay is preferably above 2 but below 7, and for best results the clay should have a pH in the neighborhood of 3 to 5. While more acid clays may be employed, their use tends to promote the formation of unsaponifiable components in the monomer.
  • Typical feed stocks for the use in the process of this invention include the fatty acids of linseed oil, saffiower oil, soybean oil, tall oil, cottonseed oil, corn oil, that is, the oils generally known as drying and semi-drying oils. Saturated acids which may be present do not interfere and are unchanged by the process.
  • the process is carried out by introducing the requisite quantities of acids, clay and water into a vessel equipped with an agitator for maintaining the clay in suspension.
  • the vessel is preferably closed and constructed to withstand the steam pressure which will be generated at the temperature employed.
  • a vessel equipped with a reflux condenser'to return the vaporized water may be employed.
  • the charge is heated to the requisite temperature, usually 230-240" and held at this temperature for approximately 4 hours or until the appropriate drop in neutralization equivalent has occurred.
  • the charge is then cooled and the pressure released to permit flashing of the water.
  • the contents are then filtered to remove the earth and the filtrate subjected to a conventional vacuum distillation to remove the nonpolymerized portion as distillate.
  • the polymeric acids are recovered as residue.
  • Example 1 Fatty acids obtained from whole soy oil by pressure splitting and bleaching but not distilling the product parts), Filtrol (4 parts) and water (2 parts) were heated in a rocking autoclave to C., and the vessel was vented to remove air. Temperature of the reaction was increased to 230 C. and maintained at 230 C. for 4 hours. The product was cooled and filtered to remove catalyst. Separation of the monomeric and polymeric acids by distillation under reduced pressure gave a polymeric acid yield of 50% of the starting acids and a monomeric acid yield of 50%. The dimeric acid had a color of 7 Gardner, a neutralization equivalent value of 304, a saponification equivalent value of 286, and an I. V.
  • Example 2 Liquid cottonseed fatty acids (100 parts), Filtrol (4 parts) and water (2 parts) were heated to 120 C. at which time the autoclave was vented to remove air. The reaction was then heated to 230 C. for 4 hours, after which the partially polymerized product was cooled and filtered to remove the catalyst. Separation of polymerized material from unreacted fatty acids showed that 55% of polymeric acid and 45% unpolymerized material was present.
  • the polymeric acid had a color of 6 Gardmet, a neutralization equivalent value of 305, a saponification equivalent value of 286, and an I. V. of whereas the monomeric acid had a color of less than 1 Gardner, a neutralization equivalent value of 298, a saponification f" K a c,
  • Example 4 Fatty acids (100 parts) which were derived from tall oil by rectification, fullers earth (3 parts), and water (2 parts) were heated to 260 C. for 2 hours in a rockingtype autoclave. After the 2-hour reaction period, the reaction mass was cooled to 120 C. and filtered to remove the earth catalyst. The partially polymerized fatty acids were separated by distillation under reduced pressure.
  • the liquid fatty acids from soya bean oil were obtained by removing the solid acid content by crystallization from solvents.
  • the liquid acids were heated to 215 C. for 4 hours in the presence of 5% of acid activated clay and 2% of water. After heating, the autoclave in which the reaction was performed was cooled to approximately 140 C., the steam pressure was released and the product filtered to remove the clay. The filtrate was distilled under 2 mm. vacuum, 56.4% of polymeric acids having an iodine value of 137.7, a neutralization equivalent of 311.8, a saponification equivalent of 296, and a color of 7 Gardner was obtained.
  • the acids used had an I. V. of 153.7 and a neutralization equivalent of 293 and a saponification equivalent of 285.
  • Example 6 Distilled safflower fatty acids were heated at 230 C. for 4 hours with 4% of Filtrol and 2% water, as described in Example 5. The results are shown in tabular form:
  • Example 7 Linseed fatty acids were processed using the same conditions as described in Example 6.
  • Filtrol A group of acid-activated adsorbents and catalysts made from the mineral montmorillonite, (Mg,Ca)OAlz5SiOznHz0. They are supplied as fine white powders, -95% passing through a 200-mesh screen.
  • the method of polymerizing polyunsaturated fatty acids which comprises heating parts by weight of polyunsaturated fatty acids with 26 parts crystalline clay mineral having a pH of 2-7 and about 15 parts water at a temperature of 215260 C. for a period of 25 hours, the exact time being such as to produce a polymeric residue having a neutralization equivalent between 10 and 25 units higher than its saponification equivalent.
  • the method of polymerizing polyunsaturated fatty acids which comprises heating 100 parts by weight of polyunsaturated fatty acids with 2-6 parts montmorillonite having a pH of about 3-5, and about 1-5 parts water at a temperature of 215-260 C. for a period of 2-5 hours, the exact time being such as to produce a polymeric residue having a neutralization equivalent between 10 and 25 units higher than its saponification equivalent.
  • the method of polymerizing polyunsaturated fatty acids to produce polycarboxylic fatty acids which comprises heating the polyunsaturated fatty acids and agitating them in the presence of a crystalline clay mineral having a pH of 2-7, the weight of the clay mineral being substantially 120% of the weight of the polyunsaturated fatty acids, and in the continuing presence of a small amount of water of the order of 1-5% of the weight of the polyunsaturated fatty acids until the neutralization equivalent of the polymerized products is reduced 7 to no more than 25 units higher than their saponification equivalent, the reaction being conducted in a temperature range of substantially ISO-260 C., the temperature which is utilized being sufficiently high to promote the reaction to the specified degree.
  • the method of polymerizing polyunsaturated fatty acids to produce polycarboxylic fatty acids which comprises heating the polyunsaturated fatty acids and agitating them in the presence of a crystalline clay mineral having a pH of 2-7, the weight of the clay mineral being substantially 1-20% of the weight of the polyunsaturated fatty acids, and in the continuing presence of a small amount of Water of the order of 15% of the weight of the polyunsaturated fatty acids until the neutralization equivalent of the polymerized products is reduced to no more than 25 units higher than their saponification equiv- 8 alent, the reaction being conducted in a temperature range of substantially 215-240" C., the temperature which is utilized being sufliciently high to promote the reaction to the specified degree, filtering the mixed acids to remove the clayand distilling the unreacted fatty acids from the residue.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)
US475006A 1954-12-13 1954-12-13 Method of making polymeric acids Expired - Lifetime US2793220A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BE543587D BE543587A (pt) 1954-12-13
NL92418D NL92418C (pt) 1954-12-13
US475006A US2793220A (en) 1954-12-13 1954-12-13 Method of making polymeric acids
GB33239/55A GB825534A (en) 1954-12-13 1955-11-21 Process of making polymeric acids
DEE11672A DE1134666B (de) 1954-12-13 1955-12-12 Verfahren zur Herstellung von zweibasischen ungesaettigten Fettsaeuren durch Dimerisieren von mehrfach ungesaettigten Fettsaeuren
FR1152544D FR1152544A (fr) 1954-12-13 1955-12-12 Perfectionnements de préparation d'acides polymérisés

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BE (1) BE543587A (pt)
DE (1) DE1134666B (pt)
FR (1) FR1152544A (pt)
GB (1) GB825534A (pt)
NL (1) NL92418C (pt)

Cited By (59)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2978468A (en) * 1957-09-23 1961-04-04 Glidden Co Polymerization, condensation and refining of fatty acids
US3065248A (en) * 1960-02-01 1962-11-20 Tallow Rescarch Inc Process for isomerization of oleic acid and its derivatives
US3157681A (en) * 1962-06-28 1964-11-17 Gen Mills Inc Polymeric fat acids
US3244596A (en) * 1962-10-18 1966-04-05 Univ Iowa College Of Pharmacy Coated medicinal agents and coating compositions therefor
US3251869A (en) * 1962-12-31 1966-05-17 Hercules Powder Co Ltd Polymeric fatty acid composition and method of making same
US3301802A (en) * 1962-04-13 1967-01-31 Emery Industries Inc Compositions comprising butadienestyrene rubber and polymerized fatty acids
US3397816A (en) * 1963-01-30 1968-08-20 Gen Mills Inc Can having seams adhesively bonded by the reaction product of alkylene diamine, alkanol amine, dicarboxylic acid, and polymeric fat acid
DE1280852B (de) * 1959-08-24 1968-10-24 Unilever Emery Verfahren zum Dimerisieren ungestaettigter Fettsaeuren
DE1280853B (de) * 1963-11-26 1968-10-24 Unilever Emery Verfahren zur Herstellung von Fettsaeurepolymerisaten durch Erhitzen von ungesaettigten hoeheren Fettsaeuren in Gegenwart von Friedel-Crafts-Katalysatoren
US3437650A (en) * 1966-11-23 1969-04-08 Hercules Inc Method of preparing tall oil fatty acid compositions
DE1292647B (de) * 1963-11-26 1969-04-17 Unilever Emery Verfahren zur Polymerisation von Fettsaeuremischungen, die wenigstens 25 Gewichtsprozent Linolensaeure enthalten
US3507890A (en) * 1966-08-24 1970-04-21 Henkel & Cie Gmbh Continuous dimerization process
US3873585A (en) * 1973-07-18 1975-03-25 Emery Industries Inc Process for the recovery of polymeric acids from clays
US3919419A (en) * 1970-05-19 1975-11-11 Oreal Insecticidal composition containing dimethyl dichlorovinyl phosphate and a polymer of polyethylene fatty acid
US4069235A (en) * 1975-01-31 1978-01-17 Agency Of Industrial Science & Technology Method for manufacture of poly-fatty acids
US4371469A (en) * 1981-04-28 1983-02-01 The United States Of America As Represented By The Secretary Of Agriculture Process for the preparation of branched chain fatty acids and esters
US4731190A (en) * 1987-02-06 1988-03-15 Alkaril Chemicals Inc. Alkoxylated guerbet alcohols and esters as metal working lubricants
US4895982A (en) * 1986-06-20 1990-01-23 Union Camp Corporation Tricarboxylic acids
US5001260A (en) * 1986-01-13 1991-03-19 Union Camp Corporation Tetracarboxylic acids
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US5064547A (en) * 1990-09-12 1991-11-12 Century Laboratories, Incoporated Lubricant compositions for metals containing dicarboxylic acids as a major constituent
US5194286A (en) * 1990-01-16 1993-03-16 The Dow Chemical Company Polybasic acid amides and their use as digestively hydrolyzable oil substitutes
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US5880298A (en) * 1993-01-18 1999-03-09 Institut Francais Du Petrole Process for oligomerization of polyunsaturated acids and esters, products obtained and use thereof
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US6187903B1 (en) 1999-07-29 2001-02-13 Cognis Corporation Method of preparing dimeric fatty acids and/or esters thereof containing low residual interesters and the resulting dimeric fatty acids and/or dimeric fatty esters
US20040067855A1 (en) * 2000-08-07 2004-04-08 Trevor Hughes Viscoelastic wellbore treatment fluid
US6835324B1 (en) * 1999-02-25 2004-12-28 Arizona Chemical Company Method for isolating oleic acid and producing lineloic dimer/trimer acids via selective reactivity
US7501479B2 (en) 2007-05-07 2009-03-10 Pittsburg State University Cationic polymerization of biological oils with superacid catalysts
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US20110008537A1 (en) * 2008-01-10 2011-01-13 Arcelormittal Investigacion Y Desarollo Sl Method for Producing an Enamelled Steel Substrate
DE112011103616T5 (de) 2010-10-28 2013-08-22 Chevron U.S.A. Inc. Kraftstoff- und Grundöl-Blendstocks aus einem einzigen Rohstoff
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US8586806B2 (en) 2010-10-28 2013-11-19 Chevron U.S.A. Inc. Fuel and base oil blendstocks from a single feedstock
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US8969259B2 (en) 2013-04-05 2015-03-03 Reg Synthetic Fuels, Llc Bio-based synthetic fluids
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US2417738A (en) * 1945-07-13 1947-03-18 Petrolite Corp Process for breaking petroleum emulsions
US2482761A (en) * 1946-07-06 1949-09-27 Emery Industries Inc Polymerization of unsaturated fatty acids

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US2347562A (en) * 1940-05-31 1944-04-25 American Cyanamid Co High molecular weight polyhydric alcohol
US2417738A (en) * 1945-07-13 1947-03-18 Petrolite Corp Process for breaking petroleum emulsions
US2482761A (en) * 1946-07-06 1949-09-27 Emery Industries Inc Polymerization of unsaturated fatty acids

Cited By (82)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2978468A (en) * 1957-09-23 1961-04-04 Glidden Co Polymerization, condensation and refining of fatty acids
DE1280852C2 (de) * 1959-08-24 1974-05-22 Unilever Emery Verfahren zum Dimerisieren ungestaettigter Fettsaeuren
DE1280852B (de) * 1959-08-24 1968-10-24 Unilever Emery Verfahren zum Dimerisieren ungestaettigter Fettsaeuren
US3065248A (en) * 1960-02-01 1962-11-20 Tallow Rescarch Inc Process for isomerization of oleic acid and its derivatives
US3301802A (en) * 1962-04-13 1967-01-31 Emery Industries Inc Compositions comprising butadienestyrene rubber and polymerized fatty acids
US3157681A (en) * 1962-06-28 1964-11-17 Gen Mills Inc Polymeric fat acids
US3244596A (en) * 1962-10-18 1966-04-05 Univ Iowa College Of Pharmacy Coated medicinal agents and coating compositions therefor
US3251869A (en) * 1962-12-31 1966-05-17 Hercules Powder Co Ltd Polymeric fatty acid composition and method of making same
US3397816A (en) * 1963-01-30 1968-08-20 Gen Mills Inc Can having seams adhesively bonded by the reaction product of alkylene diamine, alkanol amine, dicarboxylic acid, and polymeric fat acid
DE1292647B (de) * 1963-11-26 1969-04-17 Unilever Emery Verfahren zur Polymerisation von Fettsaeuremischungen, die wenigstens 25 Gewichtsprozent Linolensaeure enthalten
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FR1152544A (fr) 1958-02-19
BE543587A (pt)
DE1134666B (de) 1962-08-16
NL92418C (pt)
GB825534A (en) 1959-12-16

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