US2793220A - Method of making polymeric acids - Google Patents
Method of making polymeric acids Download PDFInfo
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- 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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- fatty acids
- acids
- equivalent
- reaction
- polyunsaturated fatty
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- 239000002253 acid Substances 0.000 title description 52
- 150000007513 acids Chemical class 0.000 title description 37
- 238000004519 manufacturing process Methods 0.000 title description 5
- 238000000034 method Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000006386 neutralization reaction Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 24
- 239000000194 fatty acid Substances 0.000 claims description 24
- 229930195729 fatty acid Natural products 0.000 claims description 24
- 150000004665 fatty acids Chemical class 0.000 claims description 24
- 238000007127 saponification reaction Methods 0.000 claims description 21
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000002734 clay mineral Substances 0.000 claims description 13
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 230000008569 process Effects 0.000 description 15
- 150000002148 esters Chemical class 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000004927 clay Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 6
- 229910052901 montmorillonite Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000003784 tall oil Substances 0.000 description 4
- 235000010469 Glycine max Nutrition 0.000 description 3
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 235000020778 linoleic acid Nutrition 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 244000068988 Glycine max Species 0.000 description 2
- 240000006240 Linum usitatissimum Species 0.000 description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 2
- 235000012216 bentonite Nutrition 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 235000012343 cottonseed oil Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 235000004426 flaxseed Nutrition 0.000 description 2
- 229910000286 fullers earth Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000005481 linolenic acid group Chemical group 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- 239000001149 (9Z,12Z)-octadeca-9,12-dienoate Substances 0.000 description 1
- WTTJVINHCBCLGX-UHFFFAOYSA-N (9trans,12cis)-methyl linoleate Natural products CCCCCC=CCC=CCCCCCCCC(=O)OC WTTJVINHCBCLGX-UHFFFAOYSA-N 0.000 description 1
- RNAMYOYQYRYFQY-UHFFFAOYSA-N 2-(4,4-difluoropiperidin-1-yl)-6-methoxy-n-(1-propan-2-ylpiperidin-4-yl)-7-(3-pyrrolidin-1-ylpropoxy)quinazolin-4-amine Chemical compound N1=C(N2CCC(F)(F)CC2)N=C2C=C(OCCCN3CCCC3)C(OC)=CC2=C1NC1CCN(C(C)C)CC1 RNAMYOYQYRYFQY-UHFFFAOYSA-N 0.000 description 1
- LNJCGNRKWOHFFV-UHFFFAOYSA-N 3-(2-hydroxyethylsulfanyl)propanenitrile Chemical compound OCCSCCC#N LNJCGNRKWOHFFV-UHFFFAOYSA-N 0.000 description 1
- KYXHKHDZJSDWEF-LHLOQNFPSA-N CCCCCCC1=C(CCCCCC)C(\C=C\CCCCCCCC(O)=O)C(CCCCCCCC(O)=O)CC1 Chemical compound CCCCCCC1=C(CCCCCC)C(\C=C\CCCCCCCC(O)=O)C(CCCCCCCC(O)=O)CC1 KYXHKHDZJSDWEF-LHLOQNFPSA-N 0.000 description 1
- 244000020518 Carthamus tinctorius Species 0.000 description 1
- 235000003255 Carthamus tinctorius Nutrition 0.000 description 1
- PKIXXJPMNDDDOS-UHFFFAOYSA-N Methyl linoleate Natural products CCCCC=CCCC=CCCCCCCCC(=O)OC PKIXXJPMNDDDOS-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000021281 monounsaturated fatty acids Nutrition 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
Classifications
-
- 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)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL92418D NL92418C (sv) | 1954-12-13 | ||
BE543587D BE543587A (sv) | 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 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US475006A US2793220A (en) | 1954-12-13 | 1954-12-13 | Method of making polymeric acids |
Publications (1)
Publication Number | Publication Date |
---|---|
US2793220A true US2793220A (en) | 1957-05-21 |
Family
ID=23885860
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US475006A Expired - Lifetime US2793220A (en) | 1954-12-13 | 1954-12-13 | Method of making polymeric acids |
Country Status (6)
Country | Link |
---|---|
US (1) | US2793220A (sv) |
BE (1) | BE543587A (sv) |
DE (1) | DE1134666B (sv) |
FR (1) | FR1152544A (sv) |
GB (1) | GB825534A (sv) |
NL (1) | NL92418C (sv) |
Cited By (59)
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 |
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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 |
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DE1211158B (de) * | 1963-06-06 | 1966-02-24 | Henkel & Cie Gmbh | Verfahren zur trans-Isomerisierung von hoehermolekularen ungesaettigten Fettsaeuren oder deren Estern |
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US2664429A (en) * | 1949-08-15 | 1953-12-29 | Emery Industries Inc | Method for manufacturing polymerized fatty acids |
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0
- NL NL92418D patent/NL92418C/xx active
- BE BE543587D patent/BE543587A/xx unknown
-
1954
- 1954-12-13 US US475006A patent/US2793220A/en not_active Expired - Lifetime
-
1955
- 1955-11-21 GB GB33239/55A patent/GB825534A/en not_active Expired
- 1955-12-12 DE DEE11672A patent/DE1134666B/de active Pending
- 1955-12-12 FR FR1152544D patent/FR1152544A/fr not_active Expired
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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 (83)
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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 |
DE1292647C2 (de) * | 1963-11-26 | 1974-01-17 | Unilever Emery | Verfahren zur Polymerisation von Fettsaeuremischungen, die wenigstens 25 Gewichtsprozent Linolensaeure enthalten |
DE1280853C2 (de) * | 1963-11-26 | 1974-03-28 | Unilever Emery | Verfahren zur Herstellung von Fettsaeurepolymerisaten durch Erhitzen von ungesaettigten hoeheren Fettsaeuren in Gegenwart von Friedel-Crafts-Katalysatoren |
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 |
US3507890A (en) * | 1966-08-24 | 1970-04-21 | Henkel & Cie Gmbh | Continuous dimerization process |
US3437650A (en) * | 1966-11-23 | 1969-04-08 | Hercules Inc | Method of preparing tall oil fatty acid compositions |
US3919419A (en) * | 1970-05-19 | 1975-11-11 | Oreal | Insecticidal composition containing dimethyl dichlorovinyl phosphate and a polymer of polyethylene fatty acid |
US3873585A (en) * | 1973-07-18 | 1975-03-25 | Emery Industries Inc | Process for the recovery of polymeric acids from clays |
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 |
US5001260A (en) * | 1986-01-13 | 1991-03-19 | Union Camp Corporation | Tetracarboxylic acids |
US4895982A (en) * | 1986-06-20 | 1990-01-23 | Union Camp Corporation | Tricarboxylic acids |
US4731190A (en) * | 1987-02-06 | 1988-03-15 | Alkaril Chemicals Inc. | Alkoxylated guerbet alcohols and esters as metal working lubricants |
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EP0771852A2 (en) | 1995-11-01 | 1997-05-07 | General Electric Company | Flame retardant thermoplastic composition containing aromatic polycarbonate resins and a rubber modified graft copolymer |
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US8013088B2 (en) | 2007-05-07 | 2011-09-06 | Pittsburg State University | Cationic polymerization of biological oils |
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US20090309064A1 (en) * | 2007-05-07 | 2009-12-17 | Mihail Ionescu | Cationic polymerization of biological oils |
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Also Published As
Publication number | Publication date |
---|---|
BE543587A (sv) | |
GB825534A (en) | 1959-12-16 |
NL92418C (sv) | |
DE1134666B (de) | 1962-08-16 |
FR1152544A (fr) | 1958-02-19 |
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