Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
1997-05-08
2001-05-08
Carr, Deborah D. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S876000, C554S141000, C554S142000, C554S167000
Reexamination Certificate
active
06229056
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to unsaturated fatty compounds with improved low-temperature behavior which are obtained by transesterifying new LS sunflower oil with methanol and hydrogenating the resulting methyl esters with the double bonds intact to form the corresponding fatty alcohols. The invention also extends to derivatives of the unsaturated fatty alcohols, to processes for their production and to their use for the production of surface-active formulations. Finally, the invention relates to the use of the new LS sunflower oil for the production of unsaturated fatty alcohols.
BACKGROUND OF THE INVENTION
Fatty compounds, more particularly unsaturated fatty alcohols, are important intermediate products for a large number of products of the chemical industry, for example for the production of surfactants and cosmetic products. An overview of this subject was published, for example, by U. Ploog et al. in Seifen-Öle-Fette-Wachse 109, 225 (1983).
Unsaturated fatty alcohols cannot be produced on the basis of petrochemical raw materials and processes. Instead, they are produced from more or less unsaturated fatty acids or methyl esters thereof based on renewable raw materials which are hydrogenated with the double bonds intact, for example in the presence of chromium- and/or zinc-containing mixed oxide catalysts [cf. Ullmann's Enzyklopaedie der technischen Chemie, Verlag Chemie, Weinheim, 4th Edition, Vol. 11, pages 436 et seq.].
Basically, unsaturated fatty alcohols can be produced in three ways:
1. Fats and oils are subjected to pressure hydrolysis with water. After removal of the water-containing glycerol, split fatty acids representing mixtures of saturated and unsaturated fatty acids are obtained. Since the co-hydrogenation of these acids is unable to influence the ratio of saturated and unsaturated components, it is only possible in this way to obtain fatty alcohols with a low iodine value below 80 and preferably in the range from 50 to 55.
2. The separation of saturated and unsaturated fatty acids by distillation is only possible with a disproportionately high outlay on equipment. In contrast to (1), however, the split fatty acids can be converted by “roll-up separation” into a predominantly saturated fatty acid cut and a predominantly unsaturated fatty acid cut. Hydrogenation of the unsaturated fatty acid cut gives technical oleyl alcohols with iodine values of around 80 to 85 which, on an industrial scale, are further processed by fractional distillation or winterizing to form products with iodine values of 90 to 100.
3. It is also possible to subject highly unsaturated vegetable oils to transesterification in which the methyl esters accumulate with a relatively small percentage of saturated homologs. Roll-up separation is neither possible nor necessary in this case because the hydrogenation directly provides highly unsaturated fatty alcohols (iodine value >100).
The three processes mentioned have long been commercially used for the production of unsaturated fatty alcohols which, unfortunately, are attended by a number of disadvantages:
The products obtainable by method 1 have an iodine value below 80 and are wax-like. Apart from the unfavorable solidification point, they do of course have only some of the advantages associated with the unsaturated structure.
Fats and oils with iodine values of 40 to 70, for example beef tallow, lard, palm oil or palm stearin, are normally used as raw materials for method 2. The resulting fatty alcohols have an iodine value of 90 to 100 and, by virtue of their property profile, are the most suitable for use on an industrial scale. However, they are often unsatisfactory both in regard to their color and in regard to their odor quality and have an unfavorably high solidification or cloud point for many applications. The same also applies to unsaturated fatty alcohols with iodine values in the same range based on conventional new sunflower oil which, on account of its high content of oleic acid, could also be used as a starting material despite its low content of polyunsaturated fatty acids.
Rapeseed oil, olive oil, linseed oil or peanut oil, for example, are suitable for the production of highly unsaturated fatty alcohols by method 3. However, highly unsaturated fatty alcohols, for example those based on new rapeseed oil low in erucic acid, contain a significant percentage of polyunsaturated homologs and, accordingly, are susceptible to autoxidation processes.
Accordingly, the problem addressed by the present invention was to provide unsaturated fatty alcohols with an iodine value of 90 to 100 based on vegetable raw materials—and corresponding derivatives—which would be distinguished in particular by improved low-temperature behavior.
DESCRIPTION OF THE INVENTION
The present invention relates to unsaturated fatty compounds with improved low-temperature behavior obtainable by
(a) transesterifying new LS sunflower oil with an oleic acid content of more than 85% by weight and a stearic acid content of less than 3% by weight with methanol and
(b) hydrogenating the resulting methyl esters in known manner to form the corresponding unsaturated fatty alcohols with iodine values of 90 to 100.
It has surprisingly been found that vegetable fatty alcohols with iodine values of 90 to 100 which not only show extremely good color and odor properties, but are also distinguished as required by particularly favorable low-temperature behavior, can be obtained by the use of new sunflower oil with a low content of stearic acid (LS=“low stearic”). A particular feature of the unsaturated fatty alcohols according to the invention compared with technical oleyl alcohol based on “conventional” new sunflower oil (i.e. a sunflower oil with an oleic acid content of about 80 to 85% by weight and a stearic acid content of less than 3% by weight) is that they have a surprisingly low cloud point (1° C. as opposed to 18° C.).
Other advantageous embodiments of the invention are derivatives which also show favorable low-temperature behavior coupled with improved odor and color properties and which are obtained in known manner by subjecting the unsaturated fatty alcohols mentioned at the beginning to
alkoxylation;
alkoxylation, sulfation and neutralization;
sulfation and neutralization; or
esterification with aliphatic carboxylic acids containing 1 to 22 carbon atoms and 0 and/or 1 to 3 double bonds.
Production process
The present invention also relates to a process for the production of unsaturated fatty compounds with improved low-temperature behavior, in which
(a) new LS sunflower oil with an oleic acid content of more than 85% by weight and a stearic acid content of less than 3% by weight is transesterified with methanol and
(b) the resulting methyl esters are hydrogenated in known manner to form the corresponding unsaturated fatty alcohols with iodine values of 90 to 100.
New LS sunflower oil
The new low-stearic (LS) sunflower oil is, for example, a commercially available vegetable oil which is marketed by the Pioneer Corporation, USA [cf. EP-A1 0 496 504, U.S. Pat. No. 5,276,264] and which has the typical composition shown in Table 1 below:
TABLE 1
Composition of New LS Sunflower Oil
Content
Fatty Acid Components
% By Weight
Palmitic acid
2 to 5
Stearic acid
0.5 to 2
Oleic acid
85 to 95
Linoleic acid
3 to 5
A particular characteristic of this new vegetable oil is that it contains more than 85% by weight and preferably more than 90% by weight of oleic acid and less than 3% by weight of stearic acid.
Transesterification
By transesterification (alcoholysis) is meant the replacement of one alcohol bound in the ester by another. The transesterification of triglycerides with methanol proceeds in accordance with reaction equation 1:
Transesterification like esterification is an equilibrium reaction. Accordingly, an excess of methanol or removal of the glycerol is recommended in order to displace the equilibrium of the reaction onto the methyl ester side.
The replacement of the glycerol component of fats by mon
Ansmann Achim
Assmann Georg
Demmering Guenther
Koehler Michael
Schuster Fritz
Carr Deborah D.
Drach John E.
Grandmaison Real J.
Henkel Kommanditgesellschaft auf Aktien
Meder Martin G.
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