MXPA01006277A - Method for producing surfactant alcohols and surfactant alcohol ethers, the resulting products and their use - Google Patents

Abstract

The invention relates to a method for producing novel surfactant alcohols and surfactant alcohol ethers by derivatising olefins with approximately 10 to 20 C-atoms or mixtures of such olefins to produce alkanols and optionally, subsequently alkoxylating them. The method is characterised in that a C4-olefin-mixture is subjected to metathesis, the resulting olefins are dimerised and then derivatised to produce surfactant alcohols, and these are optionally alkoxylated. The olefin mixture obtained from dimerisation contains a large proportion of branched components and less than 10 wt.%of compounds containing a vinylidene group. The invention also relates to the use of surfactant alcohols and surfactant alcohol ethers for producing surfactants by glycosylation or polyglycosylation, sulphation or phosphation.

Description

METHOD FOR PRODUCING TENSEACTIVE ALCOHOLS AND ETHENS OF TENSEACTIVE ALCOHOLS. THE RESULTING PRODUCTS AND YOUR EMPLOYMENT The present invention relates to a method for the preparation of surfactant alcohols and ethers of surfactant alcohols, which, among other things, are highly suitable as surfactants or for the preparation of these surfactants. In the method, starting from currents of olefins C4 olefins or mixtures of olefins, they are prepared by an exchange reaction, which are dimerized to give a mixture of olefins, having 10 to 16 carbon atoms, comprising less than 10 carbon atoms. % by weight of the compounds, which have a vinylidene group, then the olefins are derivatized to give surfactant alcohols and these alcohols are optionally alkoxylated. The invention further relates to the use of surfactant alcohols and ethers of surfactant alcohols for the preparation of surfactants by glycosylation or polyglycosylation, sulfation or phosphating. The fatty alcohols, which have chain lengths of C8 to C? 8 are used for the preparation to nonionic surfactants. They are reacted with alkylene oxides to give the corresponding fatty alcohol ethoxylates. (Chapter 2.3 in: Kosswig / Stache, "Die Tenside" [Surface Active Agents], Cari Hanser Verlag, Munich, Vienna (1993)). The chain length of the fatty alcohols influences the various properties of the surfactants, such as, for example, the ability to soak, foam, the ability to dissolve fats and the cleaning power. Fatty alcohols, which have chain lengths of Cs up to CX8 can also be used to prepare anionic surfactants, such as alkyl phosphates and alkyl ether phosphates. Instead of the phosphates, it is also possible to prepare the corresponding sulfates. (Chapter 2.2 in: Kosswig / Stache "Die Tenside" [Surface Agents], Cari Hanser Verlag, Munich Vienna (1993)). These fatty alcohols can be obtained from native sources, for example fats and oils, or also in a synthetic manner, by building blocks of constructions that have a lower number of carbon atoms. A variant here is the dimerization of an olefin, to give a product with double number of carbon atoms and its functionalization, to give an alcohol.

For the dimerization of olefins, a number of processes are known. For example, the reaction can be carried out on a heterogeneous cobalt oxide / carbon catalyst, in the presence of acids, such as sulfuric or phosphoric acid (FR 964 922). with an alkyl and aluminum catalyst (WO 97/16398) or with a dissolved nickel complex catalyst (US-A-4, 069, 273). According to the details in US-A-4 069 273, the use of nickel complex catalysts (the complex forming agent used is 1,5-cyclooctadiene or 1,1,1,5,5,5 -hexafluoropentane-2, -dione) supplies highly linear olefins, with a high proportion of dimerization products. The functionalization of the olefins to give alcohols, with construction of the carbon skeleton around a carbon atom, takes place opportunely by means of the hydroformylation reaction, which supplies a mixture of aldehydes and alcohols, which can then be hydrogenated to give alcohols. Approximately 7 million metric tons of products per year can be produced worldwide, using the hydroformylation of olefins. A review of the catalysts and reaction conditions for the hydroformylation method are provided, for example, by Beller et al., In Journal of Molecular Catalysis, A104 (1995), 17-85 and also in Ullmann's Encylopedia of Industrial Chemistry, Vol. A5 (1986), page 217 et seq., Up to page 333, and the corresponding literature references. 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 greater than 8 carbon atoms, with an average of 0.7 to 3 branches. The alkanol mixture can, for example, be prepared by the hydroformylation from mixtures of branched olefins which, on the other hand, can be obtained either by the skeleton isomerization or by the dimerization of linear, internal olefins. A given advantage of the method is that the olefin stream C3 or C4 is not used for the preparation of the dimerization charge. It is concluded from this that, according to the prior art, the olefins subjected thereto to dimerization must have been prepared from ethylene (for example by the SHOP method). Since ethylene is a relatively expensive starting material for the manufacture of surfactants, ethylene-based methods have the disadvantage of cost, compared to the methods starting from C3 and / or C4 olefin streams.

Another disadvantage of this known method is the use of mixtures of internal olefins, which can only be obtained by the isomerization of the alpha-olefins, which are required for the preparation of the branched surfactant oxo-alcohols. Such methods already lead to mixtures of isomers, which, due to the varying physical and chemical data of the components, are more difficult to handle in terms of process engineering, than pure substances. Also, an additional stage of the process is required, by virtue of which the method has one more disadvantage. The dimerization of the pure internal olefin, such as 2-pentene or 3-hexane, and the subsequent derivatization of the dimerization products, have not been previously described. The structure of the components of the oxo-alcohol mixture depends on the type of mixture of olefins that have been subjected to hydroformylation. Mixtures of olefins which have been obtained by the skeletal isomerization from the alpha-olefin mixtures lead to alkanols, which are predominantly branched at the ends of the main chain, ie at positions 2 and 3, calculated from the end of the chain. the chain in each case (page 56, last paragraph). Mixtures of olefins that have been obtained by the dimerization of olefins of short chain lengths, give, by the method described in this publication, oxo-alcohols, whose branches are greater in the middle of the main chain and, as shown by the Table IV on page 68, very predominantly in C4 and also the carbon atoms removed, in relation to the hydroxyl carbon atoms. In contrast, less than 25% of the branches are at positions C2 and C3, relative to the hydroxyl carbon atom (pages 28/29 of this document). The surface active end products are obtained from the mixtures of alkanols or by oxidation of the group -CH 2 OH, to give the carboxyl group, or by sulfation of the alkanols or their alkoxylates. Similar methods for the preparation of surfactants are described in PCT Patent Application WO 97/38957 and EP-A-787 704. Also in the methods described therein, an alpha-olefin is dimerized to give a mixture of predominantly branched vinylidene olefin dimers (WO 97/38957): Ra-CH = CH2 + Rb-CH = CH ^ CH2 CH; Ra-CH2CH2C-R + Rb-CH2CH2C-R The vinylidene compounds are then isomerized in the double bond, such that this double bond is from the end of the chain to the center and then hydroformylated to give a mixture of oxo-alcohols. The latter is then further reacted, for example by sulfation, to give surfactants. A serious disadvantage of this method is that part of the alpha-olefins. These alpha-olefins are obtained, for example, by the transition metal-catalyzed oligomerization of the ethylene, Ziegler accumulation reaction, thermal decomposition of the wax or Fischer-Tropsch methods, and, therefore, are relatively starting materials. expensive for the manufacture of surfactants. A further considerable disadvantage of this known method for the preparation of surfactants is that a skeletal isomerization in the method must be inserted between the dimerization of the alpha-olefins and the hydroformylation of the dimerization product if predominantly branched products are desired. Because they use a starting material that is relatively expensive for the manufacture of surfactants and due to the need to insert an additional process step, isomerization, this known method has a considerable disadvantage in terms of cost.

Surprisingly, we have now found that olefins and branched alcohols (oxo alcohols), which can be further processed to give highly effective surfactants - referred to below as "surfactant alcohols" - can be prepared without using either alpha-olefins or olefins, which have been prepared mainly from ethylene, but starting from currents of C4 olefins of cost effective and that also, the isomerization step can be avoided if the process is carried out according to the invention, as described below. The C4 olefin streams are mixtures consisting essentially, preferably in an amount greater than 80 to 85% by volume, in particular in an amount greater than 98% by volume, of 1-butene and 2-butene, and to an extent minor comprise, usually in an amount not greater than 15 to 20% by volume, of n-butane and isobutane, in addition to traces of C5 hydrocarbons. These mixtures of hydrocarbons are also referred to in the jargon as "refined II", they are formed as by-products in the thermal decomposition of high molecular weight hydrocarbons, for example crude oil. While low molecular weight olefins, produced in this process, ethene and propene, are suitable raw materials, for the preparation of polyethylene and polypropylene, and hydrocarbon fractions greater than C6 are used as fuels in combustion engines and for For heating purposes, the further processing of the refining II, in particular its C4 olefins, to an extent sufficient to give final value products has not been possible until now. The term of C4 olefin streams, used below, therefore, should also encompass the gas mixture referred to as the raffinate II. The method, according to the invention, presents a very favorable method, according to the process, of treating C4 olefins streams, which are produced to give valuable surfactant alcohols, from which, by several methods known per se, they can prepare nonionic or anionic surfactants. This invention provides a method for the preparation of surfactant alcohols and ethers of surfactant alcohols by the derivatization of olefins, having about 10 to 20 carbon atoms or mixtures of such olefins and, optionally, subsequent alkoxylation, this method comprises: (a) subjecting a mixture of C4 olefins to exchange, (b) separating the olefins having from 5 to 8 carbon atoms from the exchange mixture, (c) subjecting the olefins separately individually or as a dimerization mixture, to give mixtures of olefins having from 10 to 16 carbon atoms, (d) subjecting the resulting olefin mixture, optionally, after fractionation, derivatizing to give a mixture of surfactant alcohols, and (e) optionally, alkoxylating these surfactant alcohols.

The main features of the exchange, used in process step a), for example, have been described in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, volume A18, p. 235/236. Other information when carrying out the process is provided, for example, in K.

J. Ivin, "Exchange of Olefins", Academic Press, London, (1983); Houben-Weyl, E18, 1163-1223; R. L. Banks, Discovery and Development of Disproportionation of Olefins, CHEMTECH (1986), February, 112-117. The application of the exchange to the main cituents present in the C4 olefin streams, which have from 5 to 10 carbon atoms, preferably have from 5 to 8 carbon atoms, but are, in particular, 2-pentene and 3-hexane . Suitable catalysts are preferably molybdenum, tungsten or rhenium compounds. It is particularly convenient to carry out the reaction with heterogeneous catalysis, the metals of catalytic activity being used, in particular, in conjunction with supports obtained from A1203 or Si02. Examples of such catalysts are Mo03 or W03 on Si02, or Re207 on Al203. It is particularly favorable to carry out the exchange in the presence of a rhenium catalyst, since, in this case, particularly moderate reaction conditiare possible. Thus, the exchange, in this case, can be carried out at a temperature of 0 to 50 ° C and at low pressures of 0.1 to 0.2 MPa. The dimerization of the olefins or mixtures of olefins, resulting in the exchange step, gives dimerization products which, with respect to the subsequent process to the surfactant alcohols, have a particularly favorable component and a particularly advantageous composition if a catalyst is used dimerization, which contains at least one element of Subgroup VIII of the Periodic Table of the Elements, and the catalytic composition and reaction conditiare selected so as to obtain a mixture of dimers, which comprises less than 10% in weight of the compounds, which have a structural element of the formula I (vinylidene group) in which A1 and A2 are aliphatic hydrocarbon radicals Preference is given to the use of internal linear pentenes and hexenes, present in the exchange product, for dimerization. Particular preference is given to the use of 3-hexene. The dimerization can be carried out with homogeneous or heterogeneous catalysis. Preference is given to the heterogeneous process, since this, on the one hand, simplifies the removal of the catalyst, making the process more economical and, on the other hand, no waste water harmful to the environment, which usually forms during the removal of the dissolved catalysts, for example by hydrolysis. Another advantage of the heterogeneous process is that the dimerization product does not contain halogens, in particular chlorine or fluorine. Soluble catalysts homogeneously contain, in general, halides containing halide or used in combination with halogen-containing cocatalysts. Of such catalyst systems, halogen can be incorporated into the dimerization products, which adversely adversely affects the quality of the product and the subsequent process, in particular the hydroformylation, to give surfactant alcohols. For heterogeneous catalysis, the use is advantageously made of combinatiof metal oxides of Subgroup VIII with aluminum oxide in the support materials made of silicon and titanium oxides, as is known, for example, from DE-A-43 39 713. The heterogeneous catalyst can be used in a fixed bed, preferably in coarse particulate form as from particles of 1 to 1.5 mm, or in suspended form (size of particles from 0.05 to 0.5 mm). In the case of a heterologous process, the dimerization is advantageously carried out at temperatures of 80 to 200 ° C, preferably 100 to 180 ° C, at the pressure prevailing at the reaction temperature, optionally also under a protective gas , at a pressure above atmospheric, in a closed system. To achieve optimal conversions, the reaction mixture is circulated several times, with a certain proportion of the circulation product being bled continuously from the system and replaced by the starting material. In the dimerization, according to the invention, mixtures of monounsaturated hydrocarbons are obtained, the components of which have a predominantly double chain length of that of the starting olefins. Within the scope of the details given above, the dimerization catalyst and the reaction conditions are advantageously chosen, so that at least 80% of the components of the dimerization mixture are in the range of 1/4 to 3. / 4, preferably 1/3 to 2/3, of the chain length of its main chain, one or two branches adjacent to the carbon atoms. A very peculiar characteristic of the olefin mixtures, prepared according to the invention and its high proportion - usually greater than 75%, in particular greater than 80% - of the components containing branches and the low proportion - usually below 25% , in particular below 20% - of unbranched olefins. A further feature is that the branching sites of the main chain, predominantly group having (y-4) and (y_5) carbon atoms are linked, where y is the number of carbon atoms in the monomer used for the dimerization. The value of (y-5) = 0 means that there are no side chains present. In the case of Ci2 olefin mixtures, prepared according to the invention, the main chain preferably carries methyl or ethyl groups at the branching points. The position of the methyl and ethyl groups in the main chain is similarly characteristic; in the case of monosubstitution, the methyl or ethyl groups are in the P = (n / 2) -m position of the main chain, where n is the length of the main chain and m is the number of carbon atoms in the groups laterals, and in the case of disubstitution products, one substituent is in the P position and the other is in the adjacent carbon atom P + l. The proportions of the monosubstitution products (a single branch) in the olefin mixture, prepared according to the invention, are characteristically in the range of 40 to 75% by weight, and the proportions of the double branched components, in the range from 5 to 25% by weight. We have also found that dimerization mixtures can also be derived particularly well when the position of the double bond satisfies certain requirements. In these advantageous olefin mixtures, the position of the double bonds with respect to the branches is such that the ratio of the "aliphatic" hydrogen atoms to the "olefinic" hydrogen atoms is in the range of Ha? If. : H0? ßf. = (2 * n-0.5): 0.5 a (2 * n-1.9): 1.9, where n is the number of carbon atoms in the olefin obtained in the dimerization. (The "aliphatic" hydrogen atoms are defined as those that bind to the carbon atoms not involved in the double bond C = C (p-bond) and the "olefinic" hydrocarbons are those bound to a carbon atom that participates in link p.) Particular preference is given to dimerization mixtures in which the ratio of Ha? lf. : H 0? ßf. = (2 * n-1.0): 1 a (2 * n-1.9): 1.6. The novel olefin mixtures, which can be obtained by the process, according to the invention and having the structural characteristics given above, are similarly supplied by the present invention. They are useful intermediate products, in particular, for the preparation, described below, of the branched primary alcohols and surfactants, but they can also be used as starting materials in other industrial processes, starting from olefins, particularly when the end products are to have an improved biodegradability. If the olefin mixtures, according to the invention, are to be used for the preparation of surfactants, they are first derived by processes well known per se, to give surfactant alcohols. There are several methods to achieve this, comprising the addition of either direct or indirect water (hydration) to the double bond, or an addition of CO and hydrogen (hydroformylation) to the double bond of COC. The hydration of the olefins, which results from step c) of the process, is conveniently carried out by the addition of direct water with proton catalysis. An indirect route, for example, via the addition of high percentage of sulfuric acid, to give an alkanol sulfonate and the subsequent hydrolysis to give the alkanol, is, of course, also possible. The most advantageous direct water addition is carried out in the presence of an acid catalyst, in particular heterogeneous, and generally at a very high olefin partial pressure and at very low temperatures. Suitable catalysts have proved to be, in particular, phosphoric acid on supports, such as, for example, SiO 2 or Celite, or also acid ion exchangers. The selection of conditions depends on the reactivity of the olefins to be reacted and can be routinely ascertained by preliminary experiments (lit .: for example, AJ Kresge et al., J. Am. Chem. Soc. 93, 4907 (1971 ), Houben-Weyl vol 5/4 (1969), pages 102-103 and 535-539). Hydration generally leads to mixtures of primary and secondary alkanols, where secondary alkanols predominate. For the preparation of surfactants, it is more favorable to start from primary alkanols, Therefore it is preferable to hydroformilate the derivatization of the olefin mixtures, obtained from step c) by the reaction with carbon monoxide and hydrogen, in the presence of suitable catalysts, preferably containing cobalt or rhodium, to give branched primary alcohols. The present invention thus also preferably provides a process for the preparation of the primary alkanol mixtures, which are suitable, inter alia, for the subsequent process to give surfactants, by hydroformylation of olefins, which comprises using the olefin mixtures, according to the invention and described above as starting materials. A good review of the hydroformylation process with numerous other references of the literature can be found, for example, in the extensive article by Beller et al., In Journal of Molecular Catalysis, A104 (1995) 17-85 or in Ullmann's Encylopedia of Industrial Chemistry, vol A5 (1986), page 217 et seq., Page 333, and the corresponding literature references. The extensive information given here allows a person skilled in the art to hydroformer even the branched olefins, according to the invention. In this reaction, CO and hydrogen are added to the olefinic double bonds, giving mixtures of aldehydes and alkanols, according to the following reaction equation: A3 - CH = CH2 CO / H2 + catalyst (compounds n) (iso compounds) A3-CH2-CH2-CHO A3-CH (CHO) -CH3 (alkaline) A3-CH2-CH2-CH2-OH A3-CH (CH2OH) -CH3 (alkanol) A3 = hydrocarbon radical.

The molar ratio of the normal and iso compounds in the reaction mixture is usually in the range of 1: 1 to 20: 1, depending on the chosen hydroformylation process conditions and the catalyst used. The hydroformylation is usually carried out in a temperature range of 90 to 200 ° C and at a CO / H2 pressure of 2.5 to 35 MPa (25 to 350 bar). The mixing ratio of carbon monoxide to hydrogen depends on whether the preferred intention is to produce alkanals or alkanols. The CO: H2 ratio is advantageously from 10: 1 to 1:10, preferably from 3: 1 to 1: 3, where, for the preparation of the alkanals, the range of the low partial hydrogen pressures is chosen and for the For the preparation of alkanols, the range of high hydrogen partial pressures is chosen, for example, C0: H2 = 1: 2.

Suitable catalysts are mainly metal compounds of the formula HM (CO) 4 or M2 (CO) 8, where M is a metal atom, preferably a cobalt, rhodium or ruthenium atom. Generally, under hydroformylation conditions, the catalysts or catalyst precursors used in each case form catalytically active species of the formula HxMy (CO) xLq, wherein M is a metal of subgroup VIII, L is a ligature, which can be phosphine, phosphite, amine, pyridine or any other donor compound, which is included in polymeric form, and q, x, y and z are integers, which depend on the valence and type of metal and the covalence of the ligature L, where q can be also 0. The metal M is preferably cobalt, ruthenium, rhodium, palladium, platinum, osmium or iridium and, in particular, is cobalt, rhodium or ruthenium. Suitable compounds or complexes of rhodium are, for example, the salts of rhodium (II) and rhodium (III), such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium and rhodium, rhodium (II) or rhodium (III) carboxylate, rhodium (II) or rhodium (III) acetate, rhodium oxide salts (III) of rhodium (III) acid, such as, for example, tris-ammonium hexachloro-rod (III). Also suitable are rhodium complexes, such as rhodium bis-carbonylacetylacetonate, acetylacetonate-bis-ethylene-thio (I). Preference is given to the use of the rhodium biscarbonyl acetylacetonate or rhodium acetate. Suitable cobalt compounds are, for example, cobalt (II) chloride, cobalt (II) sulfate, cobalt (II) carbonate, cobalt (II) nitrate, their hydrate or amine complexes, cobalt carboxylates , such as cobalt acetate, cobalt ethylhexanoate, cobalt naphtanoate, and the cobalt caprolactam complex. Here, it is also possible to use the cobalt carbonyl complexes, such as dicobalt octocarbonyl, tetracobalt dodecarbonyl and hexacobalt hexadecacarbonyl. These cobalt, rhodium and ruthenium compounds are known in principle and are sufficiently described in the literature or they can be prepared by persons skilled in the art in a manner analogous to that for the compounds already known. The hydroformylation can be carried out with the addition of inert solvents or diluents or without such addition. Suitable inert additives are, for example, acetone, methyl ethyl ketone, cyclohexanone, toluene, xylene, chlorobenzene, methylene chloride, hexane, petroleum ether, acetonitrile, and high-boiling fractions of the hydroformylation of the products. of dimerization.

If the resulting hydroformylation product has too high a aldehyde content, it can be removed in a simple manner by hydrogenation, for example, using hydrogen in the presence of Raney nickel or using other catalysts known for hydrogenation reactions, in particular catalysts which contain copper, zinc, cobalt, nickel, molybdenum, zirconium or titanium. In the process, the aldehyde fractions are greatly hydrogenated to give alkanols. A virtually residue-free removal of the aldehyde contained in the reaction mixture can, if desired, be achieved by post-hydrogenation, for example under particularly moderate and economical conditions using an alkali metal borohydride. Mixtures of branched primary alkanols, which can be prepared by the hydroformylation of the olefin mixtures, according to the invention, are similarly provided by the present invention. The nonionic or anionic surfactants can be prepared from alkanols, according to the invention, in a different manner. The nonionic surfactants are obtained by the reaction of the alkanols with the alkylene oxides (alkoxylation) of the formula (II): O / \ CH, CH-R1 (II) wherein R1 is hydrogen or an aliphatic radical, straight or branched chain, of the formula CnH2n + ?, and n is a number from 1 to 16, preferably from 1 to 8. In particular, R1 is hydrogen, methyl or ethyl. The alkanols according to the invention can react with a single alkylene oxide species or with two or more different species. The reaction of the alkanols with the alkylene oxides forms compounds, which, in turn, carry an OH group and can, therefore, react again with an alkylene oxide molecule. Therefore, depending on the molar ratio of the alkanol to the alkylene oxide, the reaction products are obtained which have polyether chains of variable length. The polyether chains can contain from 1 to 200 alkylene oxide structural groups. Preference is given to compounds whose polyether chains contain from 1 to 10 alkylene oxide structural groups. The chains can consist of identical chain members or they can have different alkylene oxide structural groups, which differ from each other, by virtue of their radical R1. These various structural groups may be present within the chain in the random distribution or in the form of blocks. The following reaction scheme serves to illustrate the alkoxylation of the alkanols, according to the invention, using, as an example, a reaction with two different alkylene oxides, which are used in various molar quantities, x and y.

O O / \ / \ alkali R2-OH + x CH2 - CH-R1 + and CH2 - CH - R 1a R1 R 1a R2-OH [OCH2CH-] x [OCH2CH-] and -OH R1 and Rla are different radicals, within the scope of the definitions given for R1, and R2-OH is a branched alkanol, according to the invention. The alkoxylation is preferably catalyzed by strong bases, which are advantageously added in the form of an alkali metal hydroxide or an alkaline earth metal hydroxide, usually in an amount of 0.1 to 1% by weight, based on the amount of the alkanol, R2-OH (see G. Gee et al., J. Chem.-Soc. (1961), p.1345; B.Wojtch, Makromol, Chem. 66, (1966), p.180). Acid catalysis of the addition reaction is also possible. Like Bronsted acids, Lewis acids, such as, for example, A1C13 or BF3, are also suitable (see P. H. Plesch, The chemistry of Cationic Polymerization, Pergamon Press, New York (1963). The addition reaction is carried out at temperatures of about 120 to 220 ° C, preferably 140 to 160 ° C, in a sealed container. The alkylene oxide or the mixture of different alkylene oxides is introduced into the mixture of the alkanol mixture, according to the invention, and the alkali, under the vapor pressure of the alkylene oxide mixture prevailing in the temperature of chosen reaction. If desired, the alkylene oxide can be diluted by up to about 30 to 60%, using an inert gas. This leads to additional safety against the alkaline oxide explosion-type poly-addition. If a mixture of alkylene oxide is used, then the polyether chains are formed, in which the various blocks of alkylene oxide are distributed in a virtually random manner. Variations in the distribution of the building blocks along the polyether chain arise due to the various reaction rates of the components and can also be arbitrarily achieved by the continuous introduction of an alkylene oxide mixture of a composition with controlled program. If several alkylene oxides are reacted in succession, then the polyether chains, which have a block-like distribution of the alkylene oxide building blocks, are obtained. The length of the polyether chains varies within the reaction product in a random manner, around an average, which is essentially the stoichiometric value that arises from the aggregate amount. The alkoxylates that can be prepared from the mixtures of alkanol and the olefin mixtures, according to the invention, are similarly provided by the present invention. They exhibit very good surface activity and can, therefore, be used as neutral surfactants in many application areas. Starting from the mixtures of alkanol, according to the invention, it is also possible to prepare surface active glycosides and polyglycosides (oligoglycosides). These substances have very good surfactant properties. They are obtained by the simple or multiple reaction (glycosylation, polyglycosylation) with mono-, di- or poly-saccharides with the exclusion of water and with acid catalysis. Suitable acids are, for example, HCl or H2S0. As a rule, the process produces oligoglycosides having a random chain length distribution, the average degree of oligomerization being 1 to 3 saccharide radicals. In other standard syntheses, the saccharide is first acetylated with acid catalysis, with a low molecular weight alkanol, for example butanol, to give the butanol glycoside. This reaction can also be carried out with aqueous solutions of the saccharide. The lower alkanol glycoside, for example the butanol glycoside, is then reacted with the alkanol mixtures, according to the invention, to give the desired glycosides, according to the invention. After the acid catalysis has been neutralized, the excess long chain and short chain alkanols can be removed from the equilibrium mixture, for example, by distillation under reduced pressure. Another standard method proceeds by means of the O-acetyl compounds of the saccharides. The latter are converted, using hydrogen halides, preferably dissolved in glacial acetic acid, into the corresponding 0-acetylhalosaccharides, which react in the presence of acid-binding agents with the alkanols, to give acetylated glycosides. Preferred for the glycosylation of the alkanol mixtures, according to the invention, are the monosaccharides, or the hexoses, such as glucose, fructose, galactose, sugar or pentoses, such as arabinose, xylose or ribose. Particularly preferably for the glycosylation of the alkanol mixtures, according to the invention, is glucose. That is, of course, it is also possible to use mixtures of these saccharides for glycosylation. The glycosides are obtained have sugar radicals, randomly distributed., Depending on the reaction conditions. Glycosylation can also take place several times, resulting in polyglycoside chains that are added to the hydroxyl groups of the alkanols. In polyglycosylation using different saccharides, the saccharide building blocks can be randomly distributed within the chain or form blocks of the same structural groups. Depending on the chosen reaction temperature, the furanose or pyranose structures can be obtained. To improve the solubility ratios, the reaction can also be carried out in suitable solvents or diluents. Standard processes and suitable reaction conditions have been described in several publications, for example in "Ullmann's Encyclopedia of Industrial Chemistry", 5th edition, vol. A25 (1994), pages 792-793 and in the literature references given there, by K. Igarashi, Adv. Carbohydr. Chem. Biochem, 34, (1977), pp. 243-283, by Wulff and Rohle, Angew, Chem. 86, (1974), pp. 173-187, or in Karuch and Kunz, Reaktionen der organischen Chemie [Reactions in Organic Chemistry], pp. 405408, Hüthig, Heidelberg, (1976). The glycosides and polyglycosides (oligoglycosides) which can be prepared starting from the mixtures of alkanol and olefin mixtures, according to the invention, are similarly provided by the present invention. Both the alkanol mixtures, according to the invention, and the polyethers, prepared therefrom, can be converted into anionic surfactants, esterifying (sulfating) these in a manner known per se., with sulfuric acid or sulfuric acid derivatives, to give alkyl alkyl sulfates or alkyl ether sulfates, or with phosphoric acid or its derivatives, to give alkyl alkyl phosphates or alkyl ether phosphates. Sulfation reactions of alcohols have already been described, for example in US-A-3 462 525, 3 420 875 or 3 524 864. The details in carrying out this reaction can be found in "Ullmann's Encylopedia of Industrial Chemistry ", 5th edition, vol A25 (1994), pages 779-783 and in the literature references given there.

If the sulfuric acid is used for the esterification, then from 75 to 100% strength by weight, preferably from 85 to 98% strength by weight, the acid is used (the so-called "concentrated sulfuric acid" or "monohydrate"). The esterification can be carried out in a solvent or diluent, if one wishes to control the reaction, for example, heat evolution. In general, the alcohol reagent is initially introduced, and the sulfation agent is added gradually with continuous mixing. If complete esterification of the alcohol component is desired, the sulfation agent and the alkanol are used in a molar ratio of 1: 1 to 1: 1.5, preferably 1: 1 to 1: 1.2. Minor amounts of the sulfation agent may be advantageous if the alkanol alkoxylate mixtures according to the invention are used and the intention is to prepare combinations of neutral and anionic surfactants. The esterification is usually carried out at temperatures from room temperature to 85 ° C, preferably in the range of 45 to 75 ° C. In some cases, it may be advantageous to carry out the esterification in a solvent and diluent of low boiling point, immiscible in water, at its boiling point, the formation of water, during the esterification being distilled and azeotropically separated.

Instead of the sulfuric acid of the concentration given above, for sulfating the alkanol mixtures, according to the invention, it is also possible, for example, to use sulfur trioxide, sulfur trioxide complexes, sulfur trioxide solutions in sulfuric acid ("oil"), chlorosulfonic acid, sulfuryl chloride or even amidosulfuric acid. The reaction conditions are then adapted appropriately. If the sulfur trioxide is used as the sulfation agent, then the reaction can also advantageously be carried out in a falling film reactor, countercurrent, if desired, also continuously. Following the esterification, the mixtures are neutralized by adding alkali and, optionally, after removing the excess of alkali sulfate and any solvent present, it is made. The alkanol acid sulfates and the alkanol ether sulfates and their salts, obtained by the sulfation of alkanols and alkanol ethers, according to the invention, and mixtures thereof, are similarly provided by the present invention.

In an analogous manner, alkanols and alkanol ethers, according to the invention, and mixtures thereof, can also react (phosphatize) to give acidic phosphoric esters. Suitable phosphating agents are mainly phosphoric acid, polyphosphoric acid and phosphorus pentoxide, but also P0CL3, when the functions of the remaining acid chloride are subsequently hydrolyzed. The phosphating of alcohols has been described, for example, in Synthesis 1985, pages 449 to 488. The alkanoic acid phosphates and the alkanol ether phosphates, obtained by phosphating the alkanols and alkanol ethers, according to the invention, and their mixtures are also provided by the present invention. Finally, the use of the mixtures of alkanol ether, alkanol glycosides and sulfates and acid phosphates of the alkanol mixtures and of the alkanol ether mixtures, which can be prepared from the olefin mixtures, according to the invention as Surfactants are also provided by the present invention. The following working examples illustrate the preparation and use of surfactants, according to the invention.

EXAMPLE 1 Preparation of C5 / C6 olefins from olefin streams, by exchange A C4 fraction of butadiene, having a total butene content of 84.2% by weight and a molar ratio of 1-butene: 2-butene of 1.06 (" refined II ") was continuously passed, at 40 ° C and 10 bars, through a tubular reactor loaded with a heterogeneous catalyst of Re2? 7 / A1203 The space velocity was adjusted to 4500 kg / m2 * h). The reactor discharge was distilled off and contained the following components (figures in mass percent): ethene: 1.15%, propene: 18.9%, butane: 15.8% 2-butene; 19.7%, 1.butene: 13.3%, i-butene: 1.00%, 2.penteno: 29.4%, methylbutene: 0.45%, 3.hexane: 20.3%.

Examples 2A and 2B: Heterogeneous catalyzed dimerization of 3-hexene 2A. Fixed bed process A reactor, which can be isothermally heated, having a diameter of 16 mm, was filled with 100 ml of a catalyst, having the following composition: 50% by weight NiO, 34% by weight Si02, 13% by weight of Ti02, 3% by weight of A1203 (as in DE-A-43 39 713), conditioned for 24 hours at 160 ° C in N2, used as particles of 1 to 1.5 mm. Five experiments were carried out, 3-hexene (99.9% strength by weight, 0.1% by weight C7 to Cu fractions) being passed through the fixed catalyst bed at a rate (WHSV), based on the volume of the reactor, 0.25 kg / l * h and bleeding from the system at a rate of 24 to 28 g / h. The parameters that varied in the individual experiments were the reaction temperature or the duration of operation of the experiment. The following Table I shows the experimental conditions for the five experiments and the results obtained.

Table I. Process conditions and results in the fixed bed process The discharged product was fractionally distilled and determination of the skeletal isomers of fraction d2 was carried out. The analysis revealed 14.2% by weight of the n-dodecenes, 31-8% by weight of the 5-methylundecenes, 29.1% by weight of the 4-ethyldecenes, 6.6% by weight of the 5,6-dimethyldecenes, 9.3% by weight of the 4-methyl-5-ethylnonenes and 3.7% by weight of the diethylcytenes.

B. Suspension Process (Fluidized Bed Process) A reactor, which can be isothermally encouraged, having a diameter of 20 mm and a volume of 157 ml, was filled with 30 g of a catalyst having the following composition: 50% by weight of NiO, 34% by weight of SiO2, 13% by weight of TiO2, 3% by weight of A1203 (as in DE-A-43 39 713), conditioned for 24 hours at 160 ° C in N2, used as a spray material from 0.05 to 0.5 mm. Six experiments, 3-hexene (99.9% strength by weight, 0.1% by weight C7 to Cu fractions were carried out (being passed through the fluidized bed of catalyst from below at a rate, based on the volume of the reactor, 0.25 kg / l * h The reaction product leaving the reactor was recycled for a long time (recycled: the amount of charge varied between 45 and 60) The parameters which varied in the individual experiments were also the reaction temperature , the amount of charge, the circulation current, the recycling regime and the WHSV of the experiment The duration of the experiment was 8 hours The following Tables 2A and 2B show the experimental conditions for the six experiments and the results obtained.

Tables 2 Experimental conditions and results of the suspension process Table 2A Experimental conditions Table 2B: Composition of the reaction product The discharged product was fractionally distilled and the determination of the skeletal isomers of the C12 fraction was carried out. The analysis revealed that 14% by weight of the n-dodecenes, 32% by weight of the methylundecenes, 29% by weight of the 4-ethyldecenes, 7% of the 5,6-dimethyldecenes, 9% by weight of the 4 -methyl-ethylnonenos and 4% of the diethylcytenes.

Example 3: Hydroformylation of the dodecene mixture, according to the invention. 750 g of the dodecene mixture, prepared as in Example 2B, were hydroformylated with 3.0 g of Co2 (CO) 8 at 185 ° C and 280 bar of C0 / H2 (volume ratio = 1: 1.5), with the addition of 75 g of H20 in a 2.5 liter autoclave, with an elevator shaker for 5 hours. The cobalt was oxidatively removed from the reaction product using 10% strength by weight acetic acid with the introduction of air at 90 ° C. The oxo product was hydrogen with the addition of 10% by weight of water in a 2.5 liter autoclave, with a riser stirrer containing 50 g of Raney nickel, at 125 ° C and a hydrogen pressure of 280 bar, for 10 hours. The reaction product was fractionally distilled. 450 g of the tridecanol fraction, prepared in this way, were post-hydrogenated with 3.5 g of NaBH 4. The OH number of the resulting tridecanol is 277 mg KOH / g. Using especH-NMR spectroscopy, a branching medium of 2.3 of methyl groups / molecule was determined, which corresponds to a branching degree of 1.3.

Example 3A: Hydroformylation of the dodecene mixture, according to the invention. 2.12 kg of the dodecene mixture, prepared as in Example 2A, were hydroformylated with 8 g of Co2 (CO) 8 at 185 ° C and 280 bars of CO / H2 (volume ratio = 1: 1), with the addition of 210 g of H20 in a 2.5-liter autoclave, with a lifting agitator, for 5 hours. The cobalt was oxidatively removed from the reaction product using 10% strength by weight acetic acid with the introduction of air at 90 ° C. The oxo product was hydrogen in a 5 liter tubular reactor, in a drip mode on a Co / Mo fixed bed catalyst at 175 ° C and a hydrogen pressure of 280 bar, with the addition of 10% by weight of Water. The alcohol mixture was prepared by distillation. The resulting tridecanol had an OH number of 279 mg KOH / g; using 1 H-NMR spectroscopy, a mean branching degree of 1.53 was measured.

Example 3B. Hydroformylation of a mixture of dodecenes, according to the invention 50 mg of rhodium bis-carbonylacetylacetonate, 4.5 g of polyethylenimine of molar mass Mw = 460,000, in which 60% of all the nitrogen atoms have been acylated with lauric acid, 800 g of a dodecene mixture, prepared as in Example 2A, and 196 g of toluene were heated to 150 ° C in a 2.5 liter autoclave, with a elevator agitator, under a pressure of 280 bar C0 / H2 (volume ratio of 1: 1), for 7 hours. The autoclave was then cooled, decompressed and emptied. Analysis of the resulting reaction product by gas chromatography revealed a conversion of 93%. The resulting oxo product was hydrogen in a 2.5-liter tubular reactor in a drip mode, on a fixed-bed catalyst at 175 ° C and a hydrogen pressure of 280 bar, with the addition of 10% by weight of water, and The resulting alcohol mixture was worked up by distillation. The resulting tridecanol had an OH number of 279 mg KOH / g; using ^ -H-NMR spectroscopy, a mean branching degree of 1.63 was measured.

Example 3C Hydroformylation of a mixture of dodecenes, according to the invention 50 mg of rhodium bis-carbonylacetylacetonate, 4.5 g of polyethylenimine of molar mass M w = 460,000, in which 60% of all nitrogen atoms have been acylated with acid lauric, 800 g of a dodecene mixture, prepared as in Example 2A, and 196 g of toluene were heated to 160 ° C in a 2.5 liter autoclave, with a riser, under a pressure of 280 bar CO / H2 (ratio in volume of 1: 1), during 7 hours. The autoclave was then cooled, decompressed and emptied. Analysis of the resulting reaction product by gas chromatography revealed a conversion of 94%. The resulting oxo product was hydrogen in a 2.5-liter tubular reactor in a drip mode, on a fixed-bed catalyst at 175 ° C and a hydrogen pressure of 280 bar, with the addition of 10% by weight of water, and The resulting alcohol mixture was worked up by distillation. The resulting tridecanol had an OH number of 279 mg KOH / g; using 1 H-NMR spectroscopy, a mean branching degree of 1.69 was measured.

Examples 4A and 4B, Preparation of fatty alcohol ethoxylates A. Fatty alcohol ethoxylate containing 7 mol of ethylene oxide. 400 g of the alkanol mixture, prepared as in Example 3, were introduced with 1.5 g of NaOH into a dry 2 liter autoclave. The contents of the autoclave were heated to 150 ° C and 616 g of ethylene oxide were forced into the autoclave under pressure. After all the ethylene oxide had been introduced into the autoclave, this autoclave was maintained at 150 ° C for 30 minutes. Following cooling, the catalyst was neutralized by adding sulfuric acid. The resulting ethoxylate is a neutral surfactant. It has a hazy point of 12 ° C, measured in accordance with DIN 53917, 1% strength by weight in 10% strength by weight for a solution of aqueous butyl diglycol. The surface tension of a solution of 1 g / liter of the substance in water is 27.3 mN / m, measured in accordance with DIN 53914.

B. Fatty alcohol ethoxylate containing 3 mol of ethylene oxide. 600 g of the alkanol mixture, prepared as in Example 3B, were introduced with 1.5 g of NaOH into a dry 2 liter autoclave. The contents of the autoclave were heated to 150 ° C and 396 g of ethylene oxide were forced into the autoclave under pressure. After all the ethylene oxide had been introduced into the autoclave, this autoclave was maintained at 150 ° C for 30 minutes. Following cooling, the catalyst was neutralized by adding sulfuric acid. The resulting ethoxylate is a neutral surfactant. It has a cloudy point of 43.5 ° C, measured in accordance with DIN 53917, 1% strength by weight in 10% strength by weight for a solution of aqueous butyl diglycol. The surface tension of a solution of 1 g / liter of the substance in water is 26.1 mN / m, measured in accordance with DIN 53914.

Examples 5A and 5B, Preparation of alkyl phosphates and alkyl ether A. Alkyl Phosphate 300 g of the alcohol mixture, prepared as in Example 3B, were heated at 60 ° C in a stirred vessel, under nitrogen, and 125 g of polyphosphoric acid were added slowly. During the addition, the temperature should not exceed 65 ° C. Towards the end of the addition, the mixture was heated to 70 ° C and further stirred at this temperature for 1 hour. The resulting product is an anionic surfactant. An aqueous solution of the substance in water has, at a concentration of 1 g / liter, a surface tension of 29.8 mN / m, measured in accordance with DIN 53914.

B. Alkyl ether phosphate 560 g of the alcohol ethoxylate mixture, prepared as in Example 4B, were heated at 60 ° C in a stirred vessel, under nitrogen, and 92 g of polyphosphoric acid were added slowly. During the addition, the temperature should not exceed 65 ° C. Towards the end of the addition, the mixture was heated to 70 ° C and further stirred at this temperature for 1 hour. The resulting product is an anionic surfactant. An aqueous solution of the substance in water has, at a concentration of 1 g / liter, a surface tension of 37.7 mN / m, measured in accordance with DIN 53914.

Claims (10)

1. CLAIMS 1. A method for the preparation of surfactant alcohols and ethers of surfactant alcohols, by the derivatization of olefins, having approximately 10 to 20 carbon atoms, or mixtures of these olefins, and, optionally, the subsequent alkoxylation, this The method comprises: (a) subjecting a mixture of C4 olefins to exchange, (b) separating the olefins having from 5 to 8 carbon atoms from the exchange mixture, (c) subjecting the separated olefins individually, or as a mixture of dimerization, to obtain mixtures of olefins having from 10 to 16 carbon atoms, (d) subjecting the resulting olefin mixture, optionally, after fractionation, to derivatization to give a mixture of surfactant alcohols, and (e) optionally, alkoxylating these surfactant alcohols.
2. 2. A method, as claimed in claim 1, comprising at least one of the following characteristics A through D: (A) in step a) of the method, the exchange is carried out in the presence of catalysts, which contain molybdenum , tungsten or rhenium; (B) in step b) of the method, olefins having 5 and 6 carbon atoms are separated; (C) in step c) of the method, the dimerization is carried out with a heterogeneous catalysis; (D) the derivation (step d) of the process) is carried out by hydroformylation.
3. 3. A method, as claimed in one of claims 1 and 2, wherein the dimerization catalyst is used, which contains at least one element of subgroup VIII of the Periodic Table of the Elements; and the catalyst composition and the reaction conditions are selected so as to obtain a mixture of dimers, which comprises less than 10% by weight of the compounds, which have a structural element of the formula I (vinylidene group): C = CH2 (A2 in which A1 and A2 are aliphatic hydrocarbon radicals.
4. 4. A method, as claimed in one of claims 1 to 3, comprising at least one of the following characteristics E and F: (E) in step c) of the process, the olefins having 5 and 6 carbon atoms, they are dimerized individually, or in a mixture; (F) in step c) of the process, 3-hexene is dimerized.
5. 5. A novel mixture of olefins, which can be prepared by steps a), b) and c) of the method of claim 1, wherein (a) the components have from 10 to 16 carbon atoms; (b) the proportion of the unbranched olefins is less than 25% by weight; (c) the proportion of the components, which have a structural element of the formula I (vinylidene group): C = CH2 (I) wherein A1 and A2 are aliphatic hydrocarbon radicals, is below 10% by weight.
6. 6. A mixture of olefins, as claimed in claim 5, comprising at least one of the following characteristics, G to I: (G) G) At least 80% of the components of the dimerization mixture have, in the range from 1/4 to 3/4 of the chain length of its main chain, one branch or two branches to adjacent carbon atoms; (H) at the branching sites of the main chain, predominantly groups having (y-4) and (y-5) carbon atoms are bonded, where y is the number of carbon atoms in the monomer used for the dimerization . (I) the ratio of aliphatic to olefinic hydrogen atoms is in the range of Halif: H0? ßf. = (2n-0.5): 0.5 to (2n-1.9): 1.9, where n is the number of carbon atoms in the olefin obtained in the dimerization.
7. 7. Surfactant alcohols that can be prepared by steps a), b), c), d) and, optionally, e) of the method of claim 1, wherein (a) have from 11 to 17 carbon atoms and (b) they comprise a proportion of unbranched alcohols from below 25% by weight and their alkoxylation products.
8. 8. The use of the alkoxylation products of surfactant alcohols according to claim 7, as nonionic surfactants.
9. 9. The use of surfactant alcohols and their alkoxylation products, according to claim 7, for the preparation of surfactants.
10. 10. The use of the surfactant alcohol and its alkoxylation products, according to claim 9, for the preparation of any alkanol glycoside and mixtures of polyglucosides, by the single or multiple reaction (glycosylation, polyglycosylation) with mono-, di- or polysaccharides, with the exclusion of water and with acidic catalysts or with O-acetyl saccharide halides, or of sulfates which are surface active by their esterification with sulfuric acid or sulfuric acid derivatives, to provide alkyl sulfates or acid alkyl ether sulfates, or surface active phosphates, by their esterification with the phosphoric acid or its derivatives, to supply alkyl phosphates or acid alkyl ether phosphates.