MXPA96002250A - Method of conjuging double links in oils descend - Google Patents

Abstract

The present invention relates to: providing a method for conjugating desiccant oil with double bonds so that relatively cheap linseed oil, for example, can replace the naturally conjugated and more expensive aleurite oil that has been used up to now. The conjugation is carried out by the use of ruthenium as a catalyst, formic acid or the like providing a synergistic increase in the reaction. The conjugate oil can have many uses, but the main objective is to provide a way to improve a phenolic resin adhesive used on wood or wood products.

Description

"METHOD OF CONJUGATING DOUBLE LINKS IN DESICCANT OILS ' INVENTOR: RONALD T. SLEETER.

NATIONALITY: NORTH AMERICAN CITIZEN RESIDENCE: 4666 FARIES PARKWAY DACATUR, ILLINOIS 62526 E.U.A.

OWNER: ARCHER DANIELS MIDLAND COMPANY NATIONALITY: NORTH AMERICAN SOCIETY.

RESIDENCE: 4666 FARIES PARKWAY DECATUR, ILLINOIS 62526 E.U.A.

BACKGROUND OF THE INVENTION This is a continuation in part of the application Serial No. 08 / 402,109, registered on March 10, 1995. The invention relates to new and improved desiccant oils and more particularly to said oils having better drying qualities and even more particularly to these oils having such superior drying qualities that allow them to be used as part of an improved bonding system for various wood and fiber products. "Desiccant oils" are triglycerides that have the ability to dry or polymerize. Some examples of drying oils are: flaxseed, fish, soybean, talo, aleurite, castor bean and oiticica. The drying oils are composed of fatty acids having a preponderance of two or three double bonds. The drying ability of these oils is related to their Iodine Value ("IV"), which is a quantitative measure of the number of double bonds they contain. The oils in the limit of 195 - 170 IV are fast drying, relatively. Oils within the limits of 140 - 120 IV are semi-drying, and oils with IV s less than 120 are non-drying. "Desiccant oils" include conjugated oils. The term "conjugation" is used herein to describe triglycerides that have double bonds in adjacent carbon atoms.

For natural oils that contain more than one carbon-to-carbon double bond, the double bonds are generally separated by a methylene group, commonly referred to as "methylene interruption". These fats and oils have nutritional benefits, - however, methylene interruptions limit their use in industrial polymerization applications where they could be used as coatings, adhesives and others. For these fats and oils to be used industrially, they need to polymerize quickly. For this to occur it is advantageous to have the double bonds adjacent to one another or "conjugates" (i.e., the methylene is displaced or relocated). A simple explanation of this displacement of the methylene interruption is illustrated by the following example, showing only the carbon atoms: -C = C-C-C = C- -C = C-C = C-C- The carbon chain on the left has methylene inter-rupture between the two carbon atoms that have double bonds. The carbon chain on the right is conjugated by displacement of the methylene group at the end of the chain of carbon atoms. For these vegetable oils to be useful industrially, they need to be polymerized quickly. This can be achieved by combining the double bonds to produce rapidly polymerizable oils. Over the years, many methods have been developed to produce conjugated oils by displacement of the methylene breakdown between the double bonds. Unfortunately, only limited commercial quantities of these modified vegetable oils have been produced, using the methods due to their costs and other limitations. Additionally, as far as is known, desiccant oils have not played an important role as part of the adhesive or bonding systems, generally. However, the present invention converts vegetable oils to a form with a multitude of previously unknown and unanticipated uses including their use in bonding systems, especially - but not exclusively - for bonding diverse wood materials, shavings, fibers and compounds . More particularly, it has been found that these modified vegetable oils are useful in making oriented and improved braided planks ("OSB"), planked planks, plywood, and their like. While wood is one of the most significant renewable resources on earth, the supply of trees with large diameters is decreasing. As a result, the production of OSB and other wood compounds is becoming very important both for costs and for environmental reasons. As a comparison, the manufacture of plywood uses only about 60-70% of the trunk of the tree whereas the OSB can use up to 90% of the trunk of the tree. Wood composite products require adhesives as bonding systems. In spite of the compound, wood fibers, chips and fillers are usually bonded with phenolic resins, di-phenylmethylene polymeric diisocyanates, protein gums, etc. More particularly, when it is made to OSB or particulate boards, wood and an adhesive are placed in a press that applies heat and pressure, and in which the temperature, time and pressure are each a function of the compound that is produced . DESCRIPTION OF THE INVENTION This invention produces conjugated desiccant oils which are synergistic coadhesives when used as a portion of a bonding system with phenolic resins, diisocyanates, etc. They impart substantial benefit by producing planks having about twice the strength of the planks prepared without them. Therefore, a rapid and economical process for the conjugation of oils is desirable to impart better drying characteristics to common vegetable oils and to produce conjugated oils capable of improving the binding of resins to wood products and the like.

The aleurite oil is a naturally conjugated oil and is used as a main oil for finishes of fine woods. However, it is expensive, it has to be imported, and its supply from year to year is not reliable. It would be more advantageous to modify readily available commercial vegetable oils by converting them into conjugated oils. Several candidates could be considered to replace the aleurite oil. Flaxseed oil is the first choice due to its high levels of unsaturation (IV = 155 - 205), especially linoleic acid which generally exceeds 55% by weight. Flaxseed has well-known agronomic properties and is sown in large quantities. Soybean and safflower oil are the other two candidates. However, they are generally considered to be less desirable because they have less total unsaturation and most of the unsaturated fatty acids are linoleic (IV = 120-141 and 145, respectively). The previous methods for the conjugation of double bonds produce low conversions that require long reaction times at high temperatures. This low yield favors the subsequent polymerization of the conjugated products that are being formed, further lowering the yield. The conjugation of the oil proceeds through an optimum conversion performance at the point where the polymerization exceeds the conjugation and the amount of conjugated oil descends as the reaction proceeds. This eventually produces an oil of such high viscosity that it becomes useless for many applications. Some of these procedures that produce low levels of conjugation are presented in the following list: Catalyst General Performance Reference Nickel / Carbon 34% Ind. And Eng. Chem. 997-1002 (1946), S.B. Radlove, H.M. Teeter, W.H. Bonds, J.C. Co an and J.P. Kass Primary Alcohols 19% US Patent 2,242,230 (May 20, 1941), George Burr Aliphatic Iodides 30% US Patent Organic 2,422,112 (November 12, 1946), Anderson Ralston and Otto Turinsky Inorganic Iodides 24% US Patent 2,411,113 (November 12, 1946), Anderson Ralston and Otto Turinsky S02 11% US Patent 3,278,567 (October 11, 1966), Walter E. Ratjen, Lo ell O. Cummings and John A. Kneeland Aryl thioles 18% of organic sulfur 3, 784,537 (January 8, 1974); US Patent 3,925,342, (December 9, 1975), Roland Pierre, Franz Scharrer 37% Hydroiodides amino 2,411,111, (November 12, 1946), Anderson W. Ralston and Otto Turinsky S0CL2 from esters Little Yukagaku 1970, 153-7, Hisako Shiina and Tetsutaro Hashimoto Anthraquinone 19% JAOCS 237-243 (1948), L.B. Falkenburg, Wm. DeJong, D P. Handke and S.B. Radlove Álcali (of esters) 50% aprox.G.S.R. Sastry, B.G.K. Murthy, J.S. Aggar al, manufacture of paints 32-4 (1970) Alkali (Potassium of 38% B.S. Sreenivasan T-Butoxide) and J.B. Brown, JAOCS 35 89-92 (1958) Yoduro 40% Yukagaku 28 600-604, (1979), Yasuhiko Kubota and Tetsutaro Hashimoto Hydrosilicon with 60% US Patent Metallic catalyst 3,449,384 Ender Dehydration of 50% + Ind. Eng. Chem., risino oil Prod. Dev. 16 107-111 (1977) There are several methods that have produced high levels of conjugation without concomitant polymerization. These reactions are quite efficient and produce highly conjugated products with less polymerization. Therefore, these oils are quite fluid. Some of these methods are described in the following documents: Catalyst General Performance Reference Chromium carbonyls 45-65% JAOCS 47, 33-36 (1969), B.N. Frankel Pentacarbonyl 95% JAOCS 44. 37-9 Iron (1967), U.S. Pat. 3,373,175, U.S. Pat. 3,392,177, E.N. Frankel Rodio / Iridium 50% European patent EP organometallic and 80+ O 160 544 A Basu, complex Sumit Bhaduri, T.K.G. Kasar Ruthenium on carbon European Patent EP 0 040 577, Georges Cecchi and Eugene Ucciani Rhodium / Ruthenium complexes 80% + Patent Gorman organochlor Stein 2 049 937 Helmut Singer, Werner and Herbert Lepper Most of the previous methods described in the previous documents have significant disadvantages. The carbonyls are very toxic and it is difficult to work with them. Iron pentacarbonyl is flammable at room temperature. The reaction requires a high pressure vessel capable of withstanding 1500 PSI and 200 ° C. The recovery of this one is very slow and a significant loss of catalyst not recovered inside the oil makes it very expensive. The organo-rhodium and organ-iridium catalysts are very expensive starting with the price of the metal in addition to the added expense of the synthesis of the organic complex. These reactions require 12 hours of reaction time and substantial amount of catalyst. Although it has been reported that the catalyst recovers with good performance when using a non-polar solvent, this causes an additional process cost, together with the danger of the use of flammable solvents. In addition, the amount of residual catalyst remaining in the oil after the recovery step has not been determined, but is thought to be too high to make the process economical. It has been found that carbon ruthenium, as Cechi and Ucciani practiced in European Patent Application No. 0 040 577, was not able to be reused as established in the clauses. It is critical for a process of this nature to withstand numerous reuses due to the cost of the catalyst. The activity of the catalyst for the use of the catalyst of this patent is halved for each reuse, when it is used for the conjugation of linseed oil. Typical conversions start at a conjugation of 85% for the first reaction, about 40% conjugation for the second reaction with the catalyst only used once, and about 20% conjugation for the third reaction with the catalyst used twice . Therefore, for commercial practical products, the Cecchi-Ucciani process leads to a prohibitively high cost to make conjugated oil, primarily, due to the loss of catalyst activity. In this way, the use of ruthenium in carbon alone is not a viable process. The use of organic chlorides of rhodium and ruthenium as catalysts (German Patent 2 049 937) converts linseed oil to high levels of conjugation (>60%). However, about 0.3% of the ruthenium is used as 22% of the component in an organic chlorine complex. The reaction temperature is governed by the decomposition of the temperature of the complex. An example is useful to illustrate the reuse of the catalyst. In this case, fatty acids from soybean oil were distilled from the catalyst. This would not be possible with triglycerides. In this way, for practical products, this process would be prohibitively expensive with this amount of ruthenium, if the catalyst can not be recovered. In another study, by A. Basu, S. Bhaduri and K.R. Sharma '"Metal Groups in Homogeneous Catalysis: Isomerization of Methyl Linoleate", Adv. Catal. (Proc. Nati, Symp. Catal.) 7th, 1985, describes the reaction of triruthium of tetracarbonyl and other compounds from a base-point reaction. The catalysts are added to an almost equivalent base. Using the techniques of this work in a commercial practical process to manufacture conjugated oils would result in a level of ruthenium consumption which would be intolerably high and prohibitively expensive. It has been discovered that most of the ruthenium organic complexes, ruthenium salts, and to a limited degree, covalent components of ruthenium and ruthenium salts in which the ruthenium is in any of its various valencies or oxidation states, The methylene conjugation that interrupts the double bonds in common vegetable oils can be catalyzed. The majority of the ruthenium compounds that can be solubilized towards the substrate (oils with high iodine values as double bond components interrupted by methylene) are or form homogeneous active catalysts to conjugate double bonds. In fact, organic compounds in general that have double bonds interrupted by methylene can be conjugated with the process of this invention. It has been found that the successful use of these forms of ruthenium depends on the presence of an acid during the reaction. The preferred acid is formic acid. Other acids, such as organic acids (eg, acetic, benzoic, hexalic) or HCL (in gaseous form) and also some low molecular weight alcohols (eg, methanol, ethanol, and isopropyl alcohol) work with ruthenium but at a much lower grade. Also combinations of these acids, such as formic acid and HCL (gaseous) can be used. Additionally, an excess of 80% conversion to conjugation with surprisingly low levels of ruthenium in the order of 10-20 ppm can be achieved. These catalysts can be used at any level, although the conversion of the double bonds interrupted by methylene to conjugated double bonds decreases in efficiency as lower levels of the catalyst based on the ruthenium content are used. Therefore, the level of ruthenium as a metal should be at least about 5 ppm and not more than about 200 ppm, based on the weight of the oil being treated.

A level of about 10-50 ppm ruthenium is preferred and, better, a level of about 10-20 ppm. On the other hand, the acid level should not be greater than about 4 percent by weight, based on the weight of the treated oil, with the lower end determined on a case-by-case basis. The preferred level of acid will be about 0.8-2.4 percent by weight. Finally, the reaction should be carried out in the absence of any significant amount of oxygen. Thus, common vegetable oils such as flaxseed oil can, according to this invention, be efficiently and economically conjugated to produce modified oils with unique drying properties. For an analysis of the extent of the reaction, the disappearance of linolenic and linoleic acids is controlled by liquid gas chromatography ("GLC"). Conveniently, the performance of the conjugation is then calculated as a percentage loss of linolenic acid. For example, pure, unreacted flaxseed oil is analyzed at 58.4% linolenic acid by GLC. A reaction that resulted in 20.0% linoleic acid is considered as having a 65.8% conjugation. (1-20.0 / 58.4 x 100) = 65.8 This calculation is very simplified because not all the compounds generated are conjugated. In addition, polymerization can occur and these compounds are "counted" as conjugated oil under this simplified analysis regime. However, this analysis is extremely useful when the reactions are followed and their relative effectiveness is measured. A second analytical method has been developed to analyze the extent of the reaction. This method uses the Fourier Infrared Transformation Spectrophotometry ("FTIR"). The measured cusp is in the wavelength band of 945-990 cm-1 which is specific for trans and conjugated isomers. It has been found that these data correlate closely with the GLC data described above. A way of using ruthenium in micro amounts of many forms and states to catalyze this reaction in the presence of acid was also discovered. Ruthenium is a unique metal capable of forming many diverse compounds and complexes. A treatise of 1373 leaves, The Rute-nio Chemistry, by Seddon and Seddon, Elsevier Science Publishers, New York, 1984, attests to this fact. Since so many ruthenium compounds exhibit catalytic activity with the present invention, it is impossible to test or enlist all of them. Therefore, examples of classes of ruthenium compounds are established that can be used to illustrate the broad limits of their possibilities. Therefore, the examples presented below should not limit this invention. Examples of useful ruthenium complexes are triruthenium dodecacarbonyl, ruthenium dichlorotris (triphenylphosphene), and ruthenium 2,4-pentanedionate (III). An example of a useful ruthenium salt is ruthenium chloride hydrate (III) which is particularly preferred in the practice of this invention. An example of a covalent compound is ruthenium dioxide. Optimally, it has been found that for the triruthenium dodecacarbonyl, a ruthenium base amount of 50 ppm catalyst converted the flaxseed oil to 75% conjugated linoleic acid and 26% conjugated linoleic acid product with a reaction temperature of 180 ° and a reaction time of 1 hour. With the triphenylphosphene, the reaction of the double bonds interrupted by methylene had increased the selectivity forming a greater proportion of trans isomers before proceeding with the conjugation. It was intensely active producing an 85.3% conjugation of linoleic acid in three hours with 10 ppm of ruthenium base and 180 ° C. The pentanedione gave a conjugation of 50.7% at 20 ppm and 180 ° C. It has been found in almost all cases that when most forms of ruthenium are allowed to contact the substrate under the reaction conditions, they will be solubilized into the substrate. as homogeneous catalysts or they will be converted into homogeneous catalysts. The solubilization and activation of ruthenium is optimally achieved with the use of formic acid. The greatest success is achieved by the presentation of ruthenium to the substrate (flaxseed oil or organic compound) in a monomolecular form. Most of the ruthenium organic complexes are soluble in the substrate allowing the dispersion of the ruthenium in molecular form. The ruthenium thus dissolved can react more and activate as highly active catalysts by formic acid and other acids and alcohols, as discussed above. The action of formic acid is not fully understood until now. It can act to reduce the ruthenium complex to dispersed metallic molecular ruthenium. The only potential catalyst that does not work was ruthenocene, ruthenium bis (cyclopentadienyl), which is an intermediate compound consisting of ruthenium between two cyclopentadiene rings. This compound did not have catalytic activity. The ruthenium in this compound is completely enclosed between the rings of the cyclopentadiene. Therefore, it is not accessible to promote catalysis. In addition, the ruthenocene was very stable to react with the formic acid to form an active catalyst under the conditions of the reaction. Therefore, it would seem that perhaps other stable ruthenium compounds in which ruthenium is not accessible could also be excluded from the practice of the invention. It is preferred in this practice that ruthenium (III) chloride hydrate be used. This compound is preferred not only because of cost and availability but also because expensive conversions to an organic ruthenium complex are not required. As an example RuC13 hydrate can be solubilized in linseed oil by previous solubilization in alcohols or organic acids such as methanol, ethanol, or formic acid. The resulting RuC13 solution can be dispersed and eventually completely dissolved in solution. For example, only 20 ppm of ruthenium was needed as RuC13 hydrate to produce an 85% conjugation of flaxseed oil. At this rate of use a commercially viable process is achieved because the cost of ruthenium loss is not prohibitive even if it does not recover. Another advantage of the present invention is the production of a product that does not need filtration or any other pre-shipment treatment for its use. The color of the oil produced is very light. In some cases, antioxidants act to prolong the life of the catalyst and to help promote synergistically greater conjugation, thus allowing the efficient use of smaller amounts of catalyst to achieve higher levels of conjugation that would not otherwise be achieved. The following examples are provided to illustrate the wide range of successful ruthenium compounds that can be used. All the following reactions were run under argon. EXAMPLE ONE Dodecacarbonyl triruthium was added to a refined and bleached linseed oil (in most of the examples the linseed oil was refined and bleached or refined, bleached and the wax was removed) on a 50 ppm ruthenium base [Ru = 47.4% of Ru3 (CO) 12]. 0.026 grams of Ru3 (CO) 12 was added to 250 grams of flaxseed oil at room temperature. The reaction mixture was heated at 180 ° C for a period of one hour. 2.2 grams of formic acid was slowly added throughout the reaction period to help catalyze the migration of double bonds. The product, analyzed by GLC, yielded a conjugate product with 75% C18-3 and 29% C18-2 conjugate. The reaction was allowed to continue to determine the total extent of conjugation that is achieved in a reasonable time. The C18-3 conjugate was 90% in three hours of total reaction time. An additional 4.4 grams of formic acid was added at the end of the reaction. E emolo Dos A reaction similar to the previous one was run with 0.010 grams of Ru3 (CO) 12 (20 ppm Ru). The conversion for the conjugated C18-3 was 55% in one hour, 66% in two hours and 73% in 3 hours. The C18-2 conjugate was 16.9% in one hour, 22.5% in two hours and 26.9% in three hours. E-example Three A third reaction was run like the previous ones but with 15 ppm of Ru. The conjugation conversion was 47.6% of conjugated C18-3 and 10.8% of conjugated C18-2 during a three-hour reaction. Example Four 5% ruthenium was used in car bon catalyst to produce a linseed oil conjugated in 75%. The primary mode of the catalysis used is ruthenium in a monomolecular form, which is then solubilized within the oil to form a homogeneous catalyst. This was demonstrated by taking the final product of this reaction containing 83.1 ppm Ru. This reaction mixture was diluted one by one with fresh unconjugated linseed oil. The resulting mixture contained 29.5% conjugated C18-3 and 5.4% conjugated C18-2. This mixture was heated at 180 ° C for one hour and 2.2 grams of formic acid was added throughout the reaction period. The final product was analyzed by GLC and found to have 48.3% conjugated C18-3 and 15.5% conjugated C18-2. This showed that the active form of the catalyst is the soluble ruthenium metal acting as a homogeneous catalyst. Therefore, it seems that almost any method of solubilizing the ruthenium metal to a monomolecular form in the oil should work as a catalyst system. Example Five Two reactions were run for three hours each with dodecacarbonyl triruthenium (20 ppm ruthenium) at 180 ° C. One reaction had Tenox 20 added in an amount of 0.5%. Samples were taken at one hour intervals. At each step, the antioxidant reaction performed better than the reaction without antioxidant.

Reaction Percentage and Percentage C18-3 C18-2 1 hr without antioxidant 34.6 8.1 1 hr with antioxidant 58.6 10.8 2 hr without antioxidant 54.8 22.6 2 hr with antioxidant 68.5 23.0 EXAMPLE Six Reaction to 250 grams of linseed oil with 20 ppm of ruthenium as ruthenium dichlorotris (triphenylphosphene) was allowed to react with the addition of formic acid. The conversion of linolenic acid was 82% in one hour and 97% in three hours. The linoleic acid conversion was 55% in one hour and 90% in three hours. Example Seven This is a reaction similar to that of Example Six, using triphenylphosphene, run with 20 ppm ruthenium with ruthenium 2,4-pentanedionate. The conjugation was not so high with 51% C18-3 in four hours. E-example Eight A reaction was run with 20 ppm of ruthenium as ruthenium (III) of hydrated chloride (41.0% Ru test). The temperature of the reaction was 180 ° C. Formic acid was added dropwise to 250 grams of blanched flaxseed oil. The conversion to conjugated oil measured by the disappearance of linolenic and linoleic acids was 61% C18-3 and 27% C18-2 in a half hour. The conjugation reached 88% for C18-3 and 51% for C18-2 in three hours. Example Nine Another reaction similar to the previous one was run with ruthenium chloride (III) with 10 ppm Ru. The conversion was 49% C18-3 and 14% C18-2 in four hours. Example Ten A reaction was run during which formic acid was added to the reaction mixture at the beginning of the reaction, and HCL gas was further bubbled, initially and at intervals of one hour. The ruthenium catalyst was solubilized from a carbon support. The HCL increased the reaction synergistically so that it was conjugated to 95% in half an hour and began to polymerize after one hour of reaction. Other organic acids work, but not as well as formic acid. The benzoic acid was replaced in a reaction with 20 ppm of Ru as hydrate of RuC13 and the conjugation was only 35% of C18-3 in four hours. Alcohols work to a certain extent to catalyze the reaction, but with less efficiency than formic acid. Ethanol was added dropwise, one drop at a time, over the reaction period, in a manner similar to the addition of formic acid, and a 21% conjugation of C18-3 occurred in four hours using 20 ppm of Ru as RuC13 hydrate. Example Eleven As a control reaction, it was allowed to react to 250 grams of linseed oil, prebleached with bleaching earth, with 20 ppm of ruthenium as Ru3 (CO) 12 at 180 ° C for several hours in an argon atmosphere. The experimental reactions were run by adding 0.1% by weight of conventional antioxidants. A general improvement in activity was observed during the first hour of reaction after which the conjugation was paired. Percentage of Conversion to Conjugation Reaction Time Control BHA BHT 1 hour 44.0 51.5 49.3 2 hours 58.6 57.9 53.4 Several different ruthenium compounds were also studied in terms of catalytic activity that could be produced by conjugating double bonds in desiccant oils, mainly flaxseed oil. First, the study was conducted on conjugation in flaxseed oil. These compounds were chosen because of their commercial availability and because they represented a crucial section of the classes of such compounds. Tests were run on these compounds to show the wide variety of molecular forms of the ruthenium compounds that yield some catalytic activity after the loss of an unconjugated oil. For example, ruthenium triacetate represents the class of ruthenium salts of fatty acids or organic acids. Ruthenium bromide is another compound that is representative of the halogen salts. Ruthenium ammonium complexes are representative of nitrogen-containing compounds. Other compounds and some more exotic ones can be studied but their cost would limit their use in practice. Example Twelve All the reactions in this example were corrected in the same way to provide a comparison. Two hundred and fifty grams of bleached flaxseed oil was treated with each of the following catalysts under a base of 10 ppm ruthenium. The reaction was run at 180 ° C for three hours under nitrogen to sub- stantially eliminate or reduce oxygen to a minimum. One ml of formic acid was added at the time the flaxseed oil reached 150 ° c. After the initial portion of 1 mi was added, additional 7 ml of formic acid was added, by dripping for the remainder of the reaction time. During this example, other ruthenium compounds that were tested for catalytic activity are: (a) ruthenium chloride (III) penta-amine chloride, [(NH3) 5RuCl] C12, produced 13% conjugation in three hours in a base of 10 ppm of Ru; (b) the ruthenium triacetate, Ru (OAc) 3, caused a conjugation of 71% in three hours on a base of approximately 50 ppm; (c) ammonium (IV), (NH4) 2RuC16 hexachlorobutenium resulted in a conjugation of 31.3% in three hours at a base of 10 ppm; (d) the ruthenium of potassium u-oxoopentachloride (IV), K4 (RuC15) 20 caused a conjugation of 18.7% in three hours with a base of 10 ppm; (e) the ruthenium of cis-dichloro-bis (2,2'-pyridine) (II), RuC12 (C10H8N2) XH20, produced a 33% conjugation in three hours at a base of 10% ppm; (f) ruthenium bromide hydrate caused 15.6% conjugation in three hours at a base of 10 ppm; (g) the ruthenium oxide hydrate, Ru02.H2O, gave 11.1% conjugation in a 10 ppm base in three hours; (h) nitrosyl ruthenium nitrate, Ru (NO) (N03) 3, gave 55.1% conjugation in a 10 ppm base; (i) additionally, other acids were studied in terms of their effectiveness. The benzoic acid was used in place of formic acid and resulted in a 25% conjugation. Glacialacetic acid was tested and produced a 23% conjugation. Oxalic acid produced 29% conjugation. All these reactions with different acids were run on a base of 20 ppm Ru; and (j) for comparison, 10 ppm of ruthenium was dissolved as ruthenium chloride hydrate (III) (6.0 mg of RuC13.2H20) in 3 ml of anhydrous ethanol and added to 250 g. of flaxseed oil after heating to 240 ° C. The addition of 7 ml of formic acid by dripping during the reaction period of 3 hours at 180 ° C produced a conjugation of 86.7%. Example Thirteen Another example of a successful method of running a reaction as described in example twelve with ruthenium chloride (III) hydrate at 180 ° C is as follows: Ruthenium (III) chloride hydrate was mixed with water to make a 13% aqueous solution. This was used directly as a catalyst for the reaction. 250 g of bleached flaxseed oil was added to the solution at room temperature using about 2 ml of ethanol to help rinse the last remaining solution in the oil. One ml of formic acid was added at 150 ° C followed by an addition of 6 ml per drop during the 3 hour reaction period. The conjugation achieved was 77.1%. The methods of examples twelve and thirteen were judged to be the simplest to disperse and solubilize ruthenium (III) chloride hydrate in linseed oil. Example Fourteen This example was run as described in examples twelve through fourteen. Other dispersants of solubilizers were tested, such as glycerin and triglycerol mono-oleate. These dispersants worked with 36% and 14% conjugations, respectively, using 10 ppm of RuC13 hydrate. The final results were not as favorable as the final result of example fourteen, where ethanol was used. Example Fifteen As an example of other oils that can be conjugated using the process of example twelve, the most important from the point of view of economy, availability, and favorable unsaturation is soybean oil. This oil was conjugated in 82% using 20 ppm of ruthenium as a trichloride hydrate at 180 ° C in 7 ml of formic acid and 250 grams of refined and bleached soybean oil. Example Sixteen Other examples of oils were also tested. An improved drying determination was made with aleurite oil, a naturally conjugated oil, which was subjected to the same reaction conditions. The aleurite oil that was used had an alpha-eleostearic acid content of 73.8% before the reaction. After a reaction time of three hours using ruthenium (III) chloride hydrate in a base of 10 ppm ruthenium, similar to the reaction conditions mentioned above, 58.3% of the alpha-eleostearic acid remained unchanged. The other 21.0% was apparently rearranged to trans isomers. Late levigation cusps were increased in the GLC analysis.

For those with experience in art it will be easy to perceive how to modify the invention. Therefore, the attached clauses will be considered as covering all equivalent structures that fall within the limit and spirit of the invention.

Claims (33)

1. NOVELTY OF THE INVENTION Having described the invention is considered as a novelty, and therefore, the content of the following clauses is claimed as property. CLAUSES 1. A method of conjugating organic compounds interrupted by methylene comprising: reacting the organic compounds interrupted by methylene in the absence of oxygen and in the presence of an acid with a ruthenium compound selected from the group consisting of ruthenium organic complexes, Ruthenium soluble metal, ruthenium salts and covalent ruthenium compounds.
2. 2. The method of clause 1, in which the ruthenium compound is an organic ruthenium complex.
3. 3. The method of clause 2, in which the ruthenium complex is selected from the group consisting of: tri-ruthenium of dodecacarbonyl, dichlorotris (triphenylphosphene) of ruthenium (II), and 2,4-pentanodionate ruthenium.
4. 4. The method of clause 3, in which the ruthenium complex is trigenediane of dodecacarbonyl.
5. 5. The method of clause 1, in which the ruthenium compound is a ruthenium salt.
6. 6. The method of clause 5, in which the ruthenium salt is ruthenium chloride hydrate (III).
7. 7. The method of clause 1, in which the ruthenium compound is a covalent ruthenium compound.
8. 8. The method of clause 7, in which the covalent ruthenium compound is ruthenium dioxide.
9. 9. The method of clause 1, wherein the ruthenium compound is ruthenium triacetate.
10. 10. The method of clause 1, wherein the ruthenium compound is ruthenium bromide hydrate.
11. 11. The method of clause 1, wherein the ruthenium compound is ruthenium chloropenta-amine chloride (III).
12. 12. The method of clause 1, where the level of ruthenium as a metal is at least about 5 ppm and not more than about 200 ppm, based on the weight of the organic compound.
13. 13. The method of clause 1, wherein the level of ruthenium as metal is about 10-50 ppm based on the weight of the organic compound.
14. 14. The method of clause 1, in which the acid is taken from the group consisting of organic acids and HCL gas.
15. 15. The method of clause 12, wherein the acid is formic acid.
16. 16. The method of clause 1, in which a combination of formic acid and gaseous HCL is used as the acid.
17. 17. The method of clause 1, in which the acid is benzoic acid.
18. 18. The method of clause 1, in which the acid is glacialacetic acid.
19. 19. The method of clause 1, in which the acid is oxalic acid.
20. 20. The method of clause 1, in which the acid is organic acid.
21. 21. The method of clause 1, in which a low molecular weight alcohol is used in place of the acid.
22. 22. The method of clause 1, in which the level of the acid is not greater than about 4% by weight, based on the weight of the organic compound.
23. 23. The method of clause 1, in which the acid level is about 0.8-2.4% by weight, based on the weight of the organic compound.
24. 24. The method of clause 1, in which the organic compound is a common vegetable oil.
25. 25. The method of clause 24, in which the common vegetable oil is flaxseed oil.
26. 26. The method of clause 18, in which the common vegetable oil is soybean oil.
27. 27. The method of clause 1, in which a conventional antioxidant is included.
28. 28. A method of conjugating vegetable oils interrupted by methylene comprising: reacting the vegetable oils interrupted by methylene in the absence of oxygen and in the presence of formic acid with a ruthenium compound selected from the group consisting of ruthenium organic complexes, soluble metal of ruthenium, ruthenium salts and covalent ruthenium compounds.
29. 29. A common modified vegetable oil interrupted by methylene prepared by reacting common vegetable oil in the absence of oxygen and in the presence of an acid with a ruthenium compound selected from the group consisting of ruthenium organic complexes, soluble metal of ruthenium, ruthenium salts and covalent compounds of ruthenium.
30. 30. A method of conjugating vegetable oils interrupted by methylene comprising the steps of: (a) selecting at least one fatty acid oil interrupted by methylene from a group consisting of linseed oil, fish, soybeans, talus, aleurite, corn, sunflower, safflower, castor and oiticica; (b) reacting the oil selected in step (a) with a ruthenium catalyst taken from a group consisting of ruthenium organic complexes, soluble ruthenium metal, ruthenium salts and covalent ruthenium compounds; (o) conducting the reoperation of step (b) in oxygen ausanaia; and (d) adding a synergist reaction enhancing material taken from the group consisting of formic acid, hydrogen gas, benzoic acid, glacialacetic acid, oxalic acid, ethanol, glycerin, and triglycerol mono-oleate.
31. 31. The method of clause 30. wherein step (b) includes bringing the materials from steps (a) and (b) to a predetermined temperature, and when the predetermined temperature is reached, adding a portion of the material from the step (d) »and then adding the remainder of said material from step (d) by increasing it along, substantially, what remains of step (b).
32. 32. The method of clause 31, wherein said predetermined temperature is within the limits of about 150 ° -200 ° C.
33. 33. The method of clause 32, wherein the time required for the step reaction ( b) is within the limits of approximately 1-4 hours IN WITNESS WHEREOF, I have signed the above description and claims of novelty of the invention, as attorney-in-fact of ARCHER DANIELS MIDLAND COMPANY., in Mexico City, Mexico the 7th day of -June 1996. ARCHER DAN11 MIDLAND COMPANY pp Lie. Joséfde Ip Sierra, Jr. Gante \ 4-5 9