Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2001-09-10
2003-05-20
Davis, Brian (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C585S001000
Reexamination Certificate
active
06566566
ABSTRACT:
The present invention relates to a process for the preparation of surfactant alcohols and surfactant alcohol ethers which, inter alia, are highly suitable as surfactants or for the preparation of surfactants. The process, starting from olefin mixtures, produces mixtures having a predominant fraction of branched decenes, which are subsequently derivatized to give surfactant alcohols and then optionally is alkoxylated.
The invention further relates to the use of the surfactant alcohols and surfactant alcohol ethers for the preparation of surfactants by glycosidation or polyglycosidation, sulfation or phosphation.
Fatty alcohols having chain lengths from C
8
to C
18
are used for the preparation of nonionic surfactants. They are reacted with alkylene oxides to give the corresponding fatty alcohol ethoxylates. (Chapter 2.3 in: Kosswig/Stache, “Die Tenside” [Surfactants], Carl Hanser Verlag, Munich Vienna (1993)). The chain length of the fatty alcohol influences various surfactant properties, such as, for example, wetting ability, foam formation, ability to dissolve grease, cleaning power.
Fatty alcohols having chain lengths from C
8
to C
18
can also be used for preparing anionic surfactants, such as alkyl phosphates and alkyl ether phosphates. Instead of phosphates, it is also possible to prepare the corresponding sulfates. (Chapter 2.2. in: Kosswig/Stache “Die Tenside” [Surfactants], Carl Hanser Verlag, Munich Vienna (1993)).
Such fatty alcohols are obtainable from native sources, e.g. from fats and oils, or else in a synthet ic ma nner by construction from building blocks having a lower number of carbon atoms. One variant here is the dimerization of an olefin to give a product having twice the number of carbon atoms and its functionalization to give an alcohol.
Linear olefins of suitable chain length are currently accessible mainly by two processes:
In the Fischer-Tropsch synthesis, as well as paraffins, olefin isomer mixtures form as coupling products.
The oligomerization of ethylene has established itself as a further source for obtaining suitable olefins on an industrial scale. In this process, the catalysts used are alkylaluminums and also homogeneous nickel catalysts, as in the case of the known SHOP process from Shell (Weissermel/Arpe, Industrielle organische Chemie [Industrial Organic Chemistry]).
Olefin fractions of suitable chain length are further processed to give surfactant alcohols. The use of ethylene has the disadvantage of high feed material costs for the monomer building block. Processes for the preparation of surfactants which are based on ethylene as starting material are therefore important economically.
For the dimerization of olefins, a number of processes are known. For example, the reaction can be carried out over a heterogeneous cobalt oxide/carbon catalyst (FR-A-1 403 273), in the presence of acids such as sulfuric or phosphoric acid (FR 964 922), with an alkylaluminum catalyst (WO 97/16398), or with a homogeneously dissolved nickel complex catalyst (U.S. Pat. No. 4,069,273). According to the details in U.S. Pat. No. 4,069,273, the use of these nickel complex catalysts (the complexing agent used being 1,5-cyclooctadiene or 1,1,1,5,5,5-hexafluoropentane-2,4-dione) gives highly linear olefins with a high proportion of dimerization products.
FR-A-1 274 529 describes the Lewis-acid-catalyzed dimerization of methylpentenes, where the Lewis acid used is boron trifluoride. This process has the disadvantage that it is difficult to separate off the catalyst from the reaction product. As a result, not only are products contaminated with catalyst residues obtained, but the catalyst loss is also considerable.
DE-A 43 39 713 relates to a process for the oligomerization of unbranched C
2
- to C
6
-olefines and to catalysts being optimized in a way that they supply in the said process as intended very high portions of linear reaction products. In examples 3 and 5 butane/butene-mixtures are oligomerized resulting in reaction mixtures comprising 62 to 78 percent by weight of octene.
Functionalization of the olefins to give alcohols with extension of the carbon skeleton about a carbon atom advantageously takes place via the hydroformylation reaction, which gives a mixture of aldehydes and alcohols, which can then be hydrogenated to give alcohols. Approximately 7 million metric tons of products per annum are produced worldwide using the hydroformylation of olefins. An overview of catalysts and reaction conditions for the hydroformylation process is given, for example, by Beller et al. in Journal of Molecular Catalysis, A104 (1995), 17-85 and also in Ullmann's Encyclopedia of Industrial Chemistry, vol. A5 (1986), page 217 et seq., page 333, and the relevant literature references.
GB-A 1,471,481 relates to a process for the hydroformylation of olefines using a cobalt containing catalyst. The olefines as applied are linear and supply consequently only a few branched oxo alcohols and aldehydes.
DE-A 196 04 466 relates to aqueous compositions comprising an alkylpolyglycoside and a polyethyleneglycol derivative of Formula I as defined. The alkyl rest contained in the polyglycoside (page 2, line 55) is said to have 8 to 18, preferably 10 to 16 C-atoms; there are no direct indications about its degree of branching. The wording of page 3, line 11, i.e., the alkyl rest as being produced from fatty alcohols itself resulting from hydrogenation of native fatty acids, allows the interpretation that they are mostly linear alkyl rests.
From WO 98/23566 it is known that sulfates, alkoxylates, alkoxysulfates and carboxylates of a mixture of branched alkanols (oxo alcohols) exhibit good surface activity in cold water and have good biodegradability. The alkanols in the mixture used have a chain length of greater than 8 carbon atoms, having on average from 0.7 to 3 branches. The alkanol mixture can be prepared, for example by hydroformylation, from mixtures of branched olefins which for their part can be obtained either by skeletal isomerization or by dimerization of internal, linear olefins.
A given advantage of the process is that no C
3
- or C
4
-olefin stream is used for the preparation of the dimerization feed. It follows from this that, according to the current prior art, the olefins subjected to dimerization therein must have been prepared from ethylene (e.g. SHOP process). Since ethylene is a relatively expensive starting material for surfactant manufacture, ethylene-based processes have a disadvantage in terms of cost compared with processes which start from C
3
- and/or C
4
-olefin streams.
The structure of the components of the oxo alkanol mixture depends on the type of olefin mixture which has been subjected to hydroformylation. Olefin mixtures which have been obtained by skeletal isomerization from alpha-olefin mixtures lead to alkanols which are branched predominantly at the ends of the main chain, i.e. in positions 2 and 3, calculated from the end of the chain in each case.
The surface-active end products are obtained from the alkanol mixtures either by oxidation of the —CH
2
OH group to give the carboxyl group, or by sulfation of the alkanols or their alkoxylates.
Similar processes for the preparation of surfactants are described in the PCT Patent Application WO 97/38957 and in EP-A-787 704. Also in the processes described therein, an alpha-olefin is dimerized to give a mixture of predominantly vinylidene-branched olefin dimers:
The vinylidene compounds are then double-bond-isomerized, such that the double bond migrates from the end of the chain further into the center, and are then subjected to hydroformylation to give an oxo alcohol mixture. The latter is then further reacted, e.g. by sulfation to give surfactants. A serious disadvantage of this process is that it starts from alpha-olefins. Alpha-olefins are obtained, for example, by transition-metal-catalyzed oligomerization of ethylene, Ziegler build-up reaction, wax cracking or Fischer-Tropsch processes and are therefore relatively expensive starting materials for the manufacture of
Jäger Hans-Ulrich
Maas Heiko
Röper Michael
Schulz Ralf
Tropsch Jürgen
BASF - Aktiengesellschaft
Davis Brian
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