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
2000-05-19
2002-11-05
Metzmaier, Daniel S. (Department: 1712)
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, C554S025000, C554S026000, C554S066000
Reexamination Certificate
active
06476081
ABSTRACT:
FIELD OF THE INVENTION
The invention relates to a novel manufacturing process for compositions that can be used as emulsifying and dispersing surfactants. It also relates to the compositions obtained and their uses.
DESCRIPTION OF THE PRIOR ART
In U.S. Pat. No. 6,221,920, the Assignee described a process for the production of a composition consisting of a mixture containing at least amides, amines, ester-amides, ester-amines, salts of amines and mono-glycerides, deriving from the monomeric, dimeric, trimeric and/or tetrameric fatty acids contained in a polymerized polyunsaturated oil, this process comprising the transamdification (and transesterification) reaction of a thermally polymerized polyunsaturated oil, with at least one aminoalcohol, used in excess.
The composition obtained could be used, without any purification, as an emulsifying and dispersing surfactant, as such or after dilution with various solvents, such as, for example, aromatic fractions, various alcohols or also certain fatty acid esters.
It was indicated that the compositions thus defined could be used in a large number of applications, for example, as emulsifying agents allowing the formation of oil-in-water or water-in-oil emulsions, depending on the nature of the oil and the respective proportions of the two constituents (the hydrophilic constituent and the hydrophobic constituent). They could also be used as dispersing agents for solids or as foam stabilizers in a liquid or in an emulsion. A particular use which was indicated consisted of forming stable dispersions of ice in hydrocarbon media, for example, in light condensates of oil.
U.S. Pat. No. 5,958,844 describes another particular application of the compositions prepared according to the process of U.S. Pat. No. 6,221,920. This application consists of using them as dispersing additives for hydrates in suspension in fluids containing at least water, a gas and a liquid hydrocarbon (under conditions where hydrates may form the water and gas), in a manner so as to facilitate transport of same.
SUMMARY OF THE INVENTION
It has now been found in a surprising fashion that it is possible to improve the properties of these compositions by subjecting the polymerized oil, before reaction with the aminoalcohol, to an operation of entraining with water vapor having the effect of deodorizing the polymerized oil and eliminating degradation products which could be present in the polymerized oils and pose problems vis-a-vis certain media in which the final compositions may be used.
DETAILED DESCRIPTION OF THE INVENTION
The invention therefore proposes a novel preparation process for compositions that can be used as emulsifying and dispersing surfactants defined by the fact that it comprises the following stages:
a) use (or preparation) of a polymerized oil by polymerization of a polyunsaturated vegetable or animal oil;
b) treatment of said polymerized oil by entrainment with water vapor; and
c) reaction of the polymerized oil thus treated with an excess of at least one aminoalcohol in the presence or not of a catalyst.
In order to prepare the compositions according to the invention, a commercial polymerized polyunsaturated oil can be used, such as the products known under the names “standolie”, “stand oils” or “bodied oils”. In this case, stage (c) of the process is carried out directly.
In a different manner, if in stage (a) one has to prepare the polymerized oil, one can start from any vegetable or animal oil having a degree of polyunsaturation sufficient to allow the polymerization, by contact of the fatty chains containing diene or triene between themselves, as is the case, for example, for linoleic and linolenic acid. As examples the following oils can be mentioned: linseed, sunflower, safflower, china wood, grapeseed, soybean or corn, or certain fish oils, as well as any other oils having high levels of linoleic and/or linolenic acid. Linseed oil is preferred in the process according to the invention
An approximate composition in fatty acids of linseed oil is as follows:
palmitic acid: 5.5% by weight
stearic acid: 3.5% by weight
oleic acid: 19.0% by weight
linoleic acid: 14.4% by weight
linolenic acid: 57.6% by weight
The polymerization of a polyunsaturated oil can be carried out according to any appropriate method, thermally or by catalytic route. The polymerization by essentially thermal route can be carried out by simple heating to approximately 300° C. under nitrogen. The heating time then determines a viscosity gradient of the polymerized oil, which can reach, after a heating time for example of 20 hours or more, a dynamic viscosity of 65 Pa.s at 20° C.
The polymerization can also be carried out 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).
When the polymerized polyunsaturated oil used in the manufacturing process according to the invention is prepared, in order to reduce the duration of the polymerization and therefore the risk of forming undesirable degradation products, provision can also be made to catalyze the polymerization of the starting polyunsaturated oil by metals, such as for example, zinc, lead, tin or copper in the form of nitrates, chlorides or stearates, or also manganese in the form of oxide or of a salt. In this respect, there can be mentioned for example the heating for 6 hours of the linseed oil with copper (II) nitrate in a proportion of 0.5 to 2% by weight relative to the starting oil described by Sil S. and Koley S. N., Department of Chemical Technology, Univ. of Calcutta (1987) 37(8), 15-22.
Among the metal catalysts used to reduce the duration of the reaction, a salt or dioxide of manganese MnO
2
can be advantageously used, for example in a proportion of 0.5 to 2% by weight relative to the starting oil. Such catalysts can in fact be left in the final product without causing problems of toxicity or compatibility with the media in which the additive will be finally used.
In all cases, in order to be able to be used in the production process according to the invention, the polymerized oils advantageously have a dynamic viscosity at 20° C. of 5 to 65 Pa.s and preferably of 10 to 20 Pa.s. They generally have an acid number of 8 to 20. Similar viscosities are generally preserved after the treatment by entraining with water vapor of stage (b), as will be described below. As regards the acid number, it is generally lowered by this treatment.
The composition of the oligomers of fatty acids contained in a polymerized linseed oil having a dynamic viscosity at 20° C. of 65 Pa.s is given hereafter, by way of example:
monomeric fatty acids: 44.10% by weight
dimeric fatty acids: 32.30% by weight
trimeric fatty acids: 14.50% by weight
higher oligomers 9.10% by weight.
These values were obtained after methanolysis of the polymerized oil, and the separation of the methyl esters of the different fatty acids (monomers, dimers, trimers and higher oligomers) was achieved by gel-permeation chromatography (GPC). The acid number of the polymerized oil is equal to 16 mg of KOH/g.
The product of the polymerization reaction, after methanolysis, can be purified by distillation in order to eliminate from it the esters fraction corresponding to the monomeric fatty acids. A mixture is then obtained which contains approximately 1% of monomeric acids, approximately 75% of dimeric acids, approximately 19% of trimeric acids and approximately 5% of higher oligomers.
In stage (b) of the process according to the invention, the polymerized oil which is used or as obtained at the end of stage (a) is subjected to an entrainment with water vapor.
In order to carry out this treatment, a stream of dry water vapor is passed over the polymerized oil to be treated, in a quantity of 5 to 30% by weight relative to the oil for example, at a temperature of 180 to 250° C., under a vacuum of 7 to 2.5 kPa and for a period of 1 to 5 hours.
The amidification reaction of the fatty acids by the primary or secondary functions of the aminoalcohols used in stage (c
Durand Isabelle
Hillion Gerard
Sinquin Anne
Velly Marie
Institut Francais du Pe'trole
Metzmaier Daniel S.
Millen White Zelano & Branigan P.C.
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