Colloid systems and wetting agents; subcombinations thereof; pro – Continuous liquid or supercritical phase: colloid systems;... – Having discontinuous gas or vapor phase – e.g. – foam:
Reexamination Certificate
1998-09-25
2001-04-24
Lovering, Richard D. (Department: 1743)
Colloid systems and wetting agents; subcombinations thereof; pro
Continuous liquid or supercritical phase: colloid systems;...
Having discontinuous gas or vapor phase, e.g., foam:
C516S027000, C516S031000, C516S033000, C516S069000, C516S915000, C554S066000
Reexamination Certificate
active
06221920
ABSTRACT:
The object of the invention is a composition that consists of a mixture that comprises at least amides, amines, ester-amides, ester-amines, amine salts, and monoglycerides that are all derived from monomeric, dimeric, trimeric, and/or tetrameric acids and a process for the production of said composition, which comprises the reaction for transamidification of a polymerized polyunsaturated oil, with an amino alcohol.
The invention also relates to the uses of this composition, particularly as an emulsifying agent, that make it possible, depending on the nature of the oil, to form an oil-in-water or water-in-oil emulsion, as an agent for dispersing solids, or as an agent for stabilizing foams in a liquid or an emulsion.
The mixture that is obtained can be used, without any purification, as an emulsifying and dispersing surface agent, in the pure state, or after dilution with various solvents such as, for example, aromatic fractions, various alcohols, or else with certain fatty acid esters.
It is known that the products that are obtained from the amidification of a mixture of fatty acid oligomers with, for example, diethanolamine, have advantageous emulsifying and dispersing properties in various applications for forming water-in-oil or oil-in-water emulsions, depending on the nature of the oil that is used and the respective proportions of these two components.
Furthermore, the articles by D. N. Bhattacharyya et al. (J. Surface Sci. Technol., Vol. 5, No. 2, pp. 187-189, 1989, and Tenside Surf. Det. 27, 5, pp. 307-311, 1990) describe the preparation of ethanolamides by reacting diethanolamine on “bodied oils” after saponification or transesterification in the form of methyl esters of oils that are polymerized thermally.
It has now been found, surprisingly enough, that it was possible to obtain, in a simple and economical manner, a product that has the same surfactant properties as the alkanolamides of standard dimers by using another source of fatty acid oligomers, and this is to directly use oils that are polymerized thermally.
The object of the invention lies in the fact that there is obtained, in a single stage, a product that is very inexpensive and that corresponds to certain surfactant characteristics, including a pronounced amphiphilic nature that makes it possible to produce water-in-oil or oil-in-water emulsions.
The elimination of several major stages such as:
standard dimerization, with activated earths, ion-exchange resins, or sulfonic acids, followed by the elimination of these catalysts;
the amidification of the fatty acid oligomers with the elimination of reaction water; and finally
the elimination by filtration of an insoluble reaction by-product that comes from the dehydration reaction of two diethanolamine molecules (when this amino alcohol is used), which provides the N,N-bis(2-hydroxyethyl) piperazine, makes it possible to reduce the synthesis time by a factor of 5 to 6.
Actually, by going the way of standard synthesis, a mean reaction time on the order of about 15 hours is generally obtained, while when the process steps of the invention are used, a total mean time of three hours is adequate.
It is known that polyunsaturated oils that are rich more particularly in dienic or trienic fatty acids are polymerized by the action of heat to form polymeric structures that are called “stand oil,” “standolie,” “bodied oil,” or, in the specific case of linseed oil, linseed oil that is thickened by heating.
This thermal polymerization can be carried out only by putting into contact with one another dienic or trienic fatty chains, such as, for example, linoleic acid and linolenic acid.
This reaction is obtained by simple thermal heating at 300° C. under nitrogen, or at 280-290° C. under reduced pressure in the presence of anthraquinone or benzoquinone (see Nisshin Oils Mills, Yokohama, Japan, Nagakura and Coll. (1975), 48 (4), 217-22) or also catalyzed by metals such as, for example, zinc, lead, tin, or copper, in the form of nitrates, chlorides, stearates, etc.
It is possible to cite as an example: heating of linseed oil with 0.5 to 2% of copper (II) nitrate for 6 hours [see Sil, S. and Koley, S. N., Department of Chemical Technology, Univ. of Calcutta (1987) 37 (8), 15-22].
The heating time depends on a viscosity gradient with polymerized linseed oil which can reach, after a heating period of more than 20 hours, a viscosity of 65 Pa.s at 20° C.
Aside from linseed oil, it is possible to obtain polymerized oils by using sunflower seed oil, safflower oil, china wood oil, grapeseed oil, soybean oil, and corn oil, as well as all the oils that have high contents of linoleic acid and/or linolenic acid.
Given below, by way of example, is the composition of fatty acid oligomers that are contained in a polymerized linseed oil that has a viscosity of 65 Pa.s at 20° C.:
monomeric fatty acids=44.10%,
dimeric fatty acids=32.30%,
trimeric fatty acids=14.50% and
high-grade oligomers=9.10%.
These values were obtained after methanolysis of the triglyceride, and their separation was done by gel permeation chromatography (GPC). The acid index of the polymerized oil is equal to 16 mg of KOH/g.
The other way of producing fatty acid dimers uses activated earths. It is possible to cite, for example, U.S. Pat. Nos. 2,347,562, 2,426,489, and 2,793,220. This approach consists in dimerizing, at a temperature of 210-230° C., oleic acids or linoleic acids in the presence of an activated earth of the family of aluminosilicates of alkaline metals and alkaline-earth metals, such as, for example, montmorillonite, sepiolite, attapulgite, or halloysite.
By using the “Emery” process from the Unilever Company (described in, for example, U.S. Pat. No. 2,835,430), a product is obtained, for example after reaction, that contains about 55% by weight of dimers and trimers of fatty acids, whereby the remainder consists mainly of stearic acid and isostearic acid, and whereby the latter consists of a mixture of products that results from the skeletal isomerization of the fatty acid molecule.
The reaction product should then be purified by distillation to eliminate the fraction of monomeric acids. Then, a mixture is obtained whose composition is on the order of 1% monomeric acids, 75% dimeric acids, 19% trimeric acids, and 5% high-grade oligomers.
It is also possible to cite the catalysis by sulfonic acids described in, for example, U.S. Pat. No. 4,391,258 from the Unilever Company, as well as by strongly acidic ion-exchange ions (see Patent Document DE-A-3 250 470 by Henkel GmbH).
Note that these various methods can be used both on the fatty acids and on their corresponding esters (for example, in the form of methyl esters, ethyl esters, propyl esters, butyl esters, etc.)
The amidification reaction of the fatty acids by a primary or secondary amine is known in the prior art and operates between 110 and 160° C. without a catalyst with elimination of water as it forms, either by using a third solvent to obtain an azeotrope or by operation without a solvent, but by elimination of water by distillation under reduced pressure (see, for example, U.S. Pat. No. 2,089,212 and the article by Harry Kroll and Herbert Nadeau in J.A.O.C.S. 34, 323-326, June 1957).
The originality of the invention lies in the fact that as a dimer source, a polymerized oil that has a viscosity of between 5 and 65 Pa.s and that is made to react with excess amino alcohol is used.
The amino alcohols that can be used are, for example, monoethanolamine, monopropanolamine, monoisopropanolamine, 1-amino-butanol, 2-amino-1-butanol, N-methylethanolamine, N-butylethanolamine, pentanolamine, hexanolamine, cyclohexanolamine, polyalcohol amines, or else polyalkoxyglycolamines, as well as amino polyols such as diethanolamine, diisopropanolamine or trihydroxymethylaminomethane. Preferably, diethanolamine will be used.
The reaction is generally carried out in the absence of a solvent and catalyst, under a nitrogen atmosphere and at a temperature that is between 100 and 200° C. and preferably at a temperature of 160° C. The rea
Durand Isabelle
Hillion Gerard
Stern Robert
Velly Marie
Institut Francais du Pe'trole
Lovering Richard D.
Millen White Zelano & Branigan P.C.
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