Organic compounds -- part of the class 532-570 series – Organic compounds – Fatty compounds having an acid moiety which contains the...
Reexamination Certificate
2000-12-26
2002-09-03
Carr, Deborah D. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Fatty compounds having an acid moiety which contains the...
C554S026000
Reexamination Certificate
active
06444831
ABSTRACT:
The invention has as its object a new process for obtaining chemical compounds that are obtained from polyunsaturated fatty substances, said compounds characterized by the presence, along the linear hydrocarbon-containing chain, of a branch of at least two carbon atoms.
These compounds are obtained by adding olefins to the polyunsaturated fatty substances that may or may not be conjugated, in the presence of an iron catalytic system.
The unsaturated codimers that are obtained can be hydrogenated, and saturated fatty substances that are characterized by a melting point that is generally below −30° C., significant thermostability, and desired surfactant properties are then obtained.
The presence of branches in the fatty substance-based compounds, mainly when these branches are located toward the center of the linear chains that comprise 14 to 18 carbon atoms, is reflected by a certain number of remarkable properties, such as, for example:
The very significant lowering of the melting points, pour points, cloud points and a considerable increase of the viscosity of the branched fatty substances relative to the same linear compounds (unbranched). This property is used in, for example, the lubricants, fats, or plasticizers where esters of fatty substances, salts or esters of branched alcohols, whose acid may be organic or mineral, are used.
The reduction of the surface and interfacial tension, characteristics still sought in the field of surfactants and emulsifiers. This reduction makes it possible to obtain very low CMC (critical micellar concentration).
The inhibition of the crystallization of branched soaps that may or may not be mixed with standard soaps, which makes it possible to obtain transparent soaps.
An increase of the hydrophilicity, which makes the branched compounds more soluble or more wettable. A possible use would be to use quaternary salts of branched fatty acids in the emollients where the softening is on a par with a certain wettability.
A modification of the surface of the molecule, a surface that is characterized by gaps that are produced by the presence of branches. The cosmetic application of this property makes it possible to consider skin cream formulas that allow water vapor to pass, for example bases that consist of branched acid esters or even esters in which the acid and the alcohol are both branched.
The increased solubility of heavy metal salts with branched acids, which makes them soluble either in water or in certain organic solvents. The applications are multiple, such as drying agents in paints, like pigments, in the extraction of metals, anticorrosion where it is possible to use salts of calcium, alkanolamines, or even amines as active agents. Likewise, the branched acid salts offer a greater compatibility of certain mineral batches with polymers, which makes it possible to increase the ratio of feedstocks in the plastics.
The bactericidal or bacteriostatic effect that is more or less pronounced according to the nature of the bacteria and the number or the magnitude of the branches makes it possible to protect the creams from bacterial attack or to replace the quaternary salts in the formulations that may or may not be basic. Another use exists as an inhibitor of water evaporation where, for example, compounds such as a branched alcohol or a branched acid monoglyceride make it possible to delay the biodegradability and therefore to conserve the inhibitor.
The reaction of olefins with butadiene or other dienes has been known for a long time and was examined several times. The codimerization of butadiene with ethylene leads to 1,4-hexadiene; codimerization of ethylene with isoprene to methyl-3 hexadiene; and, finally, by codimerization of ethylene with piperylene, vinyl-2-pentene is obtained. Many catalysts are used to carry out these reactions. It is possible to cite, for example, rhodium, ruthenium, palladium, cobalt, iron, or nickel systems. Systems with a titanium base have been described (Connel, Laurence G.-Ann. N.Y. Acad. Sci. (73), 214, 143-9) to catalyze the formation of vinylcyclobutane from ethylene and butadiene.
U.S. Pat. No. 3,927,137 and German Patent Application DE-A-39 06 434 describe the use of catalytic systems with a base of iron salts combined with imine- or diimine-type ligands for codimerizing &agr;-olefins of low molecular weight with conjugated diolefins.
In contrast, the addition of an olefin to functional dienes has rarely been described. Patent U.S. Pat. No. 3,742,080 points out the possibility of adding ethylene to dienes, of which one or two hydrocarbon-containing chain ends are substituted by halogen atoms or alkoxy groups.
It is also known that an olefin can react on a conjugated diene or triene compound according to a Diels-Alder-type reaction. For example, R. E. Beal et Coll. [JAOCS 52, 400 (1975)] described the addition of ethylene to the polyunsaturated fatty substances by simple heating to a temperature of 290° C. Thus, a compound that has an unsaturated cycle with 6 carbon atoms in its hydrocarbon-containing chain is obtained from methyl and ethylene linoleate. After hydrogenation, these compounds have advantageous properties. Their melting point, however, which is above 10° C., is still too high to allow them to be used as lubricants.
Another method for obtaining branched compounds of fatty substances is known. It consists in reacting, according to a Wittig-type reaction, a ketone, such as, for example, the methyl ester of 12-oxo octadecanoic acid with an ylide, for example, the link P(&PHgr;)
3
═CHCH
3
, where &PHgr; represents a phenyl radical. The compound CH
3
(CH
2
)
5
C(═CHCH
3
) (CH
2
)
10
COOCH
3
, which can be hydrogenated into methyl ethyl-12-octadecanoate, is then obtained [see D. G. Chasin et Coll., Chem. Phys. Lipids (71) 6, 8-30].
In nature, the presence of branched saturated compounds of fatty substances that are found in Koch bacilli, for example, or, with another length of hydrocarbon-containing chain, in mutton fat has been pointed out.
Finally, it is known that the products that are referred to as “isostearic” contain traces of compounds that carry ethyl- or vinyl-type branches.
Recently, international patent applications WO-A-91/11428, 91-11427, 91/11426, and 91/11425 describe obtaining branched fatty substance compounds by a catalytic process. The addition of olefin, such as ethylene, propylene or butene-1, to the polyunsaturated fatty substance, a linoleic acid ester, for example, is catalyzed by a system with a base of rhodium, iridium, palladium, or ruthenium. The systems with rhodium, which are the only ones to have been described in an obvious way, are not very active, however.
U.S. Pat. Nos. 5,476,956 and 5,434,282 describe the use of a very specific rhodium catalytic system that makes it possible to accelerate the addition of olefin to the fatty substance dienes, particularly conjugated dienes, by a factor of 50 to 100. This process, however, is still very difficult to apply on a large scale due to excessive rhodium consumption.
FR-B-2 766 482, in the name of the applicant, describes a cobalt catalytic system that consists in reacting simple olefins, for example ethylene and propylene, in polyunsaturated esters, for example methyl linoleate, which may or may not be conjugated, to obtain branched esters. The branched compounds that are obtained can be hydrogenated and used, among other things, as lubricant bases. In this application, a process for obtaining a codimer is described. Co-catalysts can optionally be introduced, such as, for example, transition metals of iron, nickel, copper, rhodium or palladium type. These co-catalysts make it possible to catalyze the conjugation, if a start is made from an unconjugated polyenic ester and therefore to accelerate the reaction speed.
The main improvement that this invention provides consists in a very significant increase in reactivity that is obtained by use of a catalytic system with an iron base relative to the preceding system that used primarily a cobalt system. By working in the same conditions, 1
Bach Ingrid
Hillion Gerard
Olivier Helene
Carr Deborah D.
Institut Francais du Pe'trole
Millen White Zelano & Branigan P.C.
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