DE10314562A1 - Process for the preparation of a polyether composition - Google Patents

Abstract

The present invention relates to a process for the preparation of a polyether composition comprising polyethers having a polyether chain which contains a higher proportion of alkylene oxide repeat units of oxides which are not derived from linear alpha-olefins but from branched olefins and / or olefins with non-alpha - derive a permanent double bond. The invention further relates to the polyether compositions obtained by this process and their use in the additives of fuels and lubricants.

Description

The The present invention relates to a method for producing a Polyether composition containing polyether with a polyether chain, the higher one Proportion of alkylene oxide repeat units of oxides installed contains which are not different from linear α-olefins, but of branched olefins and / or olefins with a non-α-double bond derived. The invention further relates to those using this method polyether compositions obtained and their use in the additives of fuels and lubricants.

It is known to use multimetal cyanide catalysts for the preparation of polyether compounds by alkoxylation of suitable hydroxy compounds (starters). The EP-A-0 862 947 describes a process for the preparation of double metal cyanide catalysts and their use for the production of polyether alcohols. WO 99/16775 describes crystalline multimetal cyanide complexes and their use as catalysts for the production of polyether polyols by reacting diols or polyols with ethylene oxide, propylene oxide, butylene oxide or mixtures thereof. WO 00/14045 describes a process for the preparation of fatty alcohol alkoxylates by alkoxylation of monohydric aliphatic alcohols with ethylene oxide, propylene oxide and / or butylene oxide in the presence of a double metal cyanide catalyst. None of these documents contains an indication of the suitability of multimetal cyanide catalysts for the production of polyether compounds which incorporate larger amounts of alkylene oxides which are not derived from oxides of linear 1-olefins.

The WO 00/74843 and WO 00/75845 describe platelet-shaped multimetal cyanide compounds and their use for the production of polyether alcohols. As suitable alkylene oxides for the preparation of the polyether alcohols in addition to a variety of connections also called those that are do not derive from 1,2-olefins. However, these are not considered preferred emphasized still used in one of the exemplary embodiments. In particular, it cannot be inferred from these documents that the catalysts used for the production of polyether compounds own that a larger proportion contain repeating units of alkylene oxides, which are not derived from oxides of linear 1-olefins.

carburettor and intake systems of gasoline engines, but also injection systems for fuel metering, are increasing contaminated by dust particles from the Air, unburned hydrocarbon residues from the combustion chamber and the crankcase ventilation gases led into the carburetor are caused.

to Avoiding these disadvantages are the fuel additives ("detergents") to keep clean of valves and carburettors or injection systems added. such Detergents are generally used in combination with one or several so-called carrier oils. The carrier oils serve usually not just as a basis for formulation, but practice one additional "washing function" from d. H. they support and promote often the detergents in their cleansing and pure preserving effect and so can to reduce the required Amount of detergents contribute. Viscous, high-boiling oils are usually used as carrier oils and in particular thermostable liquids are used. You overdraw they are called Metal surfaces, z. B. the inlet valves, with a thin film of liquid and prevent or delay thereby the formation and deposition of decomposition products on the Metal surfaces.

Carrier oils that are frequently used are, for example, high-boiling refined mineral oil fractions, but also synthetic liquids such as oil-soluble polyethers from alkylene oxides or adducts of alkylene oxides with alcohols. Adducts of alkylene oxides with alcohols are, for example, from the DE-A-21 29 461 known. Such carrier oils based on polyethers or adducts of alkylene oxides with short-chain alcohols as starters can be obtained simply and inexpensively, but generally show insufficient compatibility with modern detergent additives, in particular detergent additives based on polyisobutenes, so that segregation can occur ,

The EP-A-0 277 345 describes adducts of ethylene oxide, propylene oxide and / or butylene oxide with polybutyl or polyisobutyl alcohols as carrier oils for fuel and lubricant compositions. The adducts are prepared in the presence of basic catalysts.

The EP-A-0 398 100 describes fuel compositions for internal combustion engines, the alkoxi Contain lation products that are obtainable by reacting mixtures of oxo alcohols with more than 8 carbon atoms and alkylene oxides with 2 to 4 carbon atoms. Only alkylene oxides derived from linear 1,2-olefins, such as ethylene oxide, propylene oxide and 1,2-butylene oxide, are used as alkylene oxides.

The WO 00/50543 describes polyalkylene alcohol polyalkoxylates and their Use in fuels and lubricants. As suitable alkylene oxides in addition to linear 1,2-alkylene oxides, cis and trans-2,3-butylene oxide and 1,3-propylene oxide, 1,4-butylene oxide, 1,6-hexylene oxide and 1,8-octylene oxide called. In the embodiments however, will be exclusive Propylene oxide and 1,2-butylene oxide used. In addition, the alkoxylation described as a production process in the presence of basic catalysts, such as potassium hydroxide, alkoxylates of Do not produce alkylene oxides that are not based on 1,2-olefins.

All previously mentioned carrier oils at least one of the following disadvantages. They require that Use of expensive starting materials, such as propene or 1-butene; their manufacture requires long polymerization times; their tolerance with modern detergent additives, such as polyisobutene and polyisobutene derivatives, is still in need of improvement pure propene derivatives in particular are incompatible. The last aspect concerns especially the viscosity properties of the polymer portion contained in the additive. One if possible low viscosity the amount of polymer used is particularly important to the undesirable To avoid the effect of the so-called "valve plug". "Valve plugging" means that complete Loss of compression on one or more cylinders of the internal combustion engine, if - caused through deposits, e.g. B. polymeric deposits on the valve stem - not the spring forces sufficient to close the valves properly.

polyether are not only suitable as carrier oils, but also z. B. in the form of polyetheramines and polyetheramine derivatives as detergents for Fuels and lubricants.

The WO 85/01956 describes fuel and lubricant additives, the polyether polyamines contain.

The EP-A-0 244 616 describes fuel and lubricant compositions containing polybutyl or polyisobutyl amines.

The EP-A-0 356 725 describes fuels for gasoline engines that contain a polyetheramine and / or polyetheramine derivative as an additive.

The WO 00/61708 describes polyalkylene alcohol polyether amines and their Use in fuels and lubricants.

The EP-A-0 687 699 describes the preparation of hydroxy-functionalized polybutylene oxide ether compositions by polymerizing C ₄ epoxides in the presence of acid-activated clays, such as montmorillonite, as catalysts. Among other things, these are said to be suitable as intermediates for the production of fuel and lubricant additives. This process is still in need of improvement. The polyether compositions obtained in particular still have high proportions of the hydroxy compounds used as starters for the polymerization. This generally requires additional work-up for further processing into fuel and lubricant additives, as a result of which this process is economically disadvantageous.

The The present invention has for its object an improved Process for the preparation of polyether compositions for further processing to provide fuel and lubricant additives.

worin zwei der Reste R¹ bis R⁴ für C₁-C₆-Alkyl und die übrigen für Wasserstoff oder C₁-C₆-Alkyl stehen, in Gegenwart eines Multimetallcyanid-Katalysators unter Erhalt einer Polyetherzusammensetzung, enthaltend hydroxyterminierte Polyether, umsetzt.This object is achieved by a process for the preparation of a polyether composition, in which a monohydroxy compound with at least one alkylene oxide of the general formula I

wherein two of the radicals R ¹ to R ^{4 are} C ₁ -C ₆ alkyl and the rest are hydrogen or C ₁ -C ₆ alkyl, in the presence of a multimetal cyanide catalyst to give a polyether composition containing hy hydroxy-terminated polyethers.

In a suitable version the polyether composition obtained is additionally subjected to one Amino functionalization to obtain a polyether composition, which contains amino and / or polyamino-terminated polyethers.

In the context of the present invention, the expression C ₁ -C ₆ -alkyl includes straight-chain and branched C ₁ -C ₆ -alkyl groups. These include in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec.-butyl, tert.-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl , 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2 , 3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl -2-methylpropyl, etc.

Suitable longer-chain C ₈ -C ₂₀ -alkyl groups are straight-chain and branched alkyl groups. These are preferably alkyl radicals such as those found in natural fatty alcohols or alcohols which are commercially available, e.g. B. oxo alcohols occur. These include e.g. B. octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl etc.

Cycloalkyl is preferably C ₅ -C ₈ cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

The Expression heterocycloalkyl for the purposes of the present invention includes saturated, cycloaliphatic groups with generally 4 to 7, preferably 5 or 6 ring atoms in which 1 or 2 of the ring carbon atoms selected by heteroatoms from the elements oxygen, nitrogen and sulfur and which may be substituted. Exemplary for such heterocycloaliphatic groups are pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethyl-piperidinyl, imidazolidinyl, pyrazolidinyl, Oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, Piperazinyl-, tetrahydrothiophenyl, tetrahydrofuranyl, tetrahydropyranyl, Called dioxanyl.

aryl includes unsubstituted and substituted aryl groups and stands preferably for Phenyl, tolyl, xylyl, mesityl, naphthyl, fluorenyl, anthracenyl, Phenanthrenyl, naphthacenyl and especially for phenyl, tolyl, xylyl or Mesityl.

hetaryl preferably stands for Pyrrolyl, pyrazolyl, imidazolyl, indolyl, carbazolyl, pyridyl, quinolinyl, acridinyl, Pyridazinyl, pyrimidinyl or pyrazinyl.

Preferably are used to produce the polyether compositions according to the invention Alkylene oxides or alkylene oxide mixtures are used, so that the therein contained polyether at least 10 mol% repeat units of alkylene oxides of the general formula I, based on the total proportion on ether repeat units, built-in included.

Especially the polyethers preferably contain 10 to 90 mol%, particularly preferably 20 to 80 mol%, in particular 25 to 70 mol% and especially 30 to 65 mol% repeating units of alkylene oxides of the general Formula I contains built-in.

in the Within the scope of the present invention, the terms n, m-alkene oxide, n, m-epoxy and n, m-alkylene oxide, in which n and m are the carbon atoms referred to that over a single bond directly connected to each other and one each Single bond to the same oxygen atom are synonymous used.

Preferably the alkylene oxides of the general formula I are selected from 2,3-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 3-methyl-1,2-pentene oxide, 4-methyl-1,2-pentene oxide and mixtures thereof. These preferably include also obtainable by oxidation of olefin streams accessible on a large industrial scale Mixtures, the other of the aforementioned different alkylene oxides and / or olefins and / or inerts not covered by the oxidation May contain (alkanes).

Preferably the alkylene oxides of the formula I are selected from cis-2,3-butene oxide, trans-2,3-butene oxide, 2-methyl-1,2-propene oxide and mixtures thereof. These include also mixtures containing further alkylene oxides and / or saturated and unsaturated Contain hydrocarbons.

Preferably contain the polyethers of the polyether composition according to the invention at the most 70 mol%, particularly preferably at most 60 mol% and in particular at most 50 mole% repeating units of alkyl 1,2-alkene oxides such as 2-methyl-1,2-propene oxide built-in.

The Use of alkyl 1,2-alkene repeat units, in particular of 2-methyl-1,2-propene oxide repeat units in the polyether compositions according to the invention can be beneficial for setting the desired product properties his. For example, polyether compounds based on 2-methyl-1,2-propene oxide usually already at lower molecular weights than polyether compounds no built-in isobutene oxide, good effect as a carrier oil for detergents and dispersants in fuel and lubricant compositions. Preferred are polyether compounds that have at least one polyether chain comprise at least 1 mol%, particularly preferably at least 5 mol% repeat units of 2-methyl-1,2-propene oxide incorporated contains.

worin R⁵ für Wasserstoff oder C₁-C₆-Alkyl steht.In addition to the repeating units of alkylene oxides of the general formula I, the polyethers can contain further, different alkylene oxide repeating units incorporated therein. Preferred are polyethers in which the polyether chain additionally contains repeating units of alkylene oxides which are selected from compounds of the general formula II

wherein R ^{5 is} hydrogen or C ₁ -C ₆ alkyl.

Preferably the compounds of the formula II are selected from ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 1,2-pentylene oxide, 1,2-hexylene oxide and mixtures thereof. Especially the alkylene oxides of the formula II are preferably selected from 1,2-propene oxide, 1,2-butene oxide and mixtures thereof. The connections Formula II can are preferably also used in the form of mixtures which by Large-scale oxidation zugängiger olefin streams available are. these can additionally Alkylene oxides of the general formula I, of alkylene oxides of the formulas I and II different other alkylene oxides, not from the oxidation contained olefins and / or inert (alkanes) contain.

Alkylene oxide mixtures which are derived from industrially available olefin mixtures are preferably used for the production of the polyether chains. Examples of such mixtures of alkylene oxides are the oxidation or epoxidation products of olefin-rich hydrocarbon streams in which the proportion of alkylene oxides of the formula I is in the ranges given above. Preferred olefin mixtures available on an industrial scale result from the hydrocarbon splitting in petroleum processing, for example by cat cracking, such as fluid catalytic cracking (FCC), thermal cracking or hydrocracking. A preferred technical olefin mixture is the C _{4 cut} . C ₄ cuts are available, for example, by fluid catalytic cracking of gas oil, steam cracking from ethane to gas oil and in particular by steam cracking from naphtha or LPG (liquefied petroleum gas) for the production of ethene and propene. Depending on the composition of the C _{4 cut, a} distinction is made between the total C _{4 cut} , the so-called raffinate I obtained after the separation of 1,3-butadiene and the raffinate II obtained after the isobutene separation. The HC ₄ is also suitable. Fraction, ie a total C _{4 cut} , the butadiene portion of which was hydrogenated to a mixture of 1-butene and cis and trans-2-butene. Depending on the quality of the fractionation, the C ₄ cuts obtained may also contain saturated and unsaturated hydrocarbons with fewer or more carbon atoms than 4, such as propane, propene, pentanes, pentenes, hexanes, hexenes etc. These olefin mixtures can also be used to prepare Advantageously use polyether compounds.

For the method according to the invention For example, a mixture of alkylene oxides is suitable, which consists of Raffinate I was obtained and has the following composition: About 3.4 mole percent isobutane; about 7.4 mole percent n-butane; about 19.9 mol% 1,2-butene; about 7.9 mole percent 2,3-trans-butene oxide; about 4.6 mol% 2,3-cis-butene oxide and about 46.8 mole percent isobutene oxide.

Likewise a mixture of alkylene oxides, which is made from raffinate II was obtained and has the following composition: about 6.2 mol% isobutane; about 13.3 mole percent n-butane; about 55.6 mole percent 1,2-butene oxide; about 14.6 mol% 2,3-trans-butene oxide; about 8.5 mol% 2,3-cis-butene oxide and about 1.8 mole percent isobutene oxide.

Preferably is the number of alkylene oxide repeat units (degree of alkoxylation) in a range from 2 to 200, particularly preferably 4 to 150 and especially 6 to 100.

Include those according to the inventive method obtained polyether compositions polyether chains, the repeating units of two or more than two different alkylene oxides of the general Formula I and optionally the general formula II incorporated included, so can these are arranged statistically or in the form of blocks in the polyether chain be statistical sections with sections (chemically uniform) blocks can take turns.

In a preferred embodiment a minimum degree of alkoxylation of the polyethers is achieved that the Oxygen content in the at least one polyether chain at least 16.5% by weight, particularly preferably at least 17.5% by weight and in particular at least 18.5% by weight of the number average molecular weight of the Makes up polyether.

In general, a monohydroxy compound of the formula R ⁶ -OH, in which R ^{6 is} C ₈ -C ₂₀ alkyl, optionally alkylated cyclohexyl or optionally alkylated aryl, with at least one alkylene oxide of the general formula I and optionally at least one for the preparation of the polyether composition alkoxylated further alkylene oxide of the general formula II and the alkoxylate obtained, if appropriate, subsequently derivatized.

Suitable radicals R ^{6 of} the compounds R ⁶ -OH (starter) are straight-chain or branched hydrocarbon radicals having preferably 9 to 18 carbon atoms, preferably 10 to 16 carbon atoms and in particular 12 to 15 carbon atoms. Suitable are, for example, those hydrocarbon radicals which are derived from alcohols, for. B. of fatty alcohols, such as 1-octanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, cetyl alcohol or stearyl alcohol, or oxo alcohols, as is usually done by hydroformylation of linear or branched olefins with 7 to 19 carbons are obtained, or from alcohols, such as those starting from olefins having 8 to 20 carbon atoms either by ozonolysis and subsequent reduction or by epoxidation and subsequent reduction or by hydroboration and subsequent oxidative cleavage with H ₂ O ₂ or by halogenation with chlorine or Bromine and subsequent alkaline hydrolysis are obtained.

Mixtures of the abovementioned hydrocarbon radicals are also suitable as radicals R ⁶ , for example those which are derived from the abovementioned alcohols or are obtained in their preparation, such as, for. B. raw products and individual fractions, such as those obtained in the distillative processing of the raw products. Examples of suitable mixtures from which the radical R ⁶ can be derived are so-called oxo oils or oxo oil fractions, as are regularly obtained in the production of oxo alcohols.

An alcohol mixture which is obtained by trimerization of butene and subsequent hydroformylation and hydrogenation and is referred to as tridecanol N is advantageously suitable as starter R ⁶ -OH.

worin
R⁹, R¹⁰ und R¹¹ unabhängig voneinander für Wasserstoff oder C₁-C₃₀-Alkyl stehen.Suitable starters R ⁶ -OH are furthermore alicyclic and aromatic hydroxy compounds, preferably compounds of the formulas

wherein
R ⁹ , R ¹⁰ and R ¹¹ independently represent hydrogen or C ₁ -C ₃₀ alkyl.

As Starter preferred alicyclic and aromatic hydroxy compounds are cyclohexanol, phenol, the cresol isomers, isobutylphenol, isobutylcresol, Diisobutylphenol, diisobutylcresol, tert-butylphenol, tert-butylcresol, Di-tert-butylphenol, di-tert-butylcresol, isooctylphenol, diisooctylphenol, Isononylphenol, diisononylphenol, isododecylphenol, diisododecylphenol and mixtures thereof.

worin
die Reihenfolge der Alkylenoxideinheiten beliebig ist, zwei der Reste R¹ bis R⁴ für C₁-C₆-Alkyl und die übrigen für Wasserstoff oder C₁-C₆-Alkyl stehen,
R⁵ für Wasserstoff oder C₁-C₆-Alkyl steht,
R⁶ für C₈-C₂₀-Alkyl, gegebenenfalls alkyliertes Cyclohexyl oder gegebenenfalls alkyliertes Aryl steht,
X für OH oder NR⁷R⁸ steht, wobei R⁷ und R⁸ unabhängig voneinander für Wasserstoff, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl, Hetaryl, Aminoalkylen, Polyaminoalkylen, Polyoxyalkylen oder R⁷ und R⁸ gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, für einen 5- bis 8-gliedrigen Heterocyclus stehen,
n für eine ganze Zahl von 1 bis 200 und
m für eine ganze Zahl von 0 bis 200 steht,
mit der Maßgabe, dass der Quotient n/(n+m) mindestens 0,1 beträgt.The polyether composition obtained by the process according to the invention preferably contains at least one compound of the general formula III

wherein
the order of the alkylene oxide units is arbitrary, two of the radicals R ¹ to R ⁴ for C ₁ -C ₆ alkyl and the rest represent hydrogen or C ₁ -C ₆ -alkyl,
R ^{5 represents} hydrogen or C ₁ -C ₆ alkyl,
R ^{6 represents} C ₈ -C ₂₀ alkyl, optionally alkylated cyclohexyl or optionally alkylated aryl,
X represents OH or NR ⁷ R ⁸ , where R ⁷ and R ⁸ independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, aminoalkylene, polyaminoalkylene, polyoxyalkylene or R ⁷ and R ⁸ together with the nitrogen atom to which they are attached are a 5- to 8-membered heterocycle,
n for an integer from 1 to 200 and
m represents an integer from 0 to 200,
with the proviso that the quotient n / (n + m) is at least 0.1.

The Inventors of the present invention have found that in the Production of polyether compounds according to the prior art known methods, by alkoxylation of compounds with active Hydrogen atoms (so-called starters) in the presence of alkali and / or Alkaline earth metal hydroxides as catalysts alkylene oxides not of linear α-olefins derive, not or only when using uneconomically long reaction times react. When using alkylene oxide mixtures, the alkylene oxides based on linear α-olefins and those based on different olefins (higher branched or with internal double bonds), essentially react only that of linear α-olefins derived alkylene oxides. On the other hand, are activated clay used as catalysts, generally only one results incomplete Implementation of the starter used. Surprisingly, now found that these drawbacks are avoided when used for alkoxylation a so-called double metal or multimetal cyanide catalyst (hereinafter referred to as multimetal cyanide catalysts) is used.

to Preparation of a polyether composition containing polyether the at least one block with repeating units of alkylene oxides of general formula I and at least one block with repeat units contain built-in alkylene oxides of the general formula II, can only if desired building blocks of alkylene oxides I in the presence of a multimetal cyanide catalyst respectively. For building blocks A conventional catalyst can be used for alkylene oxides II become. So you can z. B. a mixture containing 1-butene oxide for Block formation first in the presence of a usual polymerize basic catalyst and after removing the basic Continue the polymerization in the presence of a multimetal cyanide catalyst.

The Use of multimetal cyanide catalysts in the process according to the invention leads in typically lead to a reduction in response time and higher sales Alkylene oxides in the alkoxylation reaction, especially if the proportion of alkylene oxides of the general formula I above 10 mol%, preferably above 20 mol% and in particular above of 30 mol%, based on the sum of all alkylene oxides used, lies. About that leads out the use of multimetal cyanide catalysts for alkoxylation products, which have a molecular weight distribution which is compatible, the effectiveness and in particular the viscosity properties for use as carrier oils and / or as detergents or dispersants in fuel and lubricant compositions additionally positively influenced.

Multimetal cyanide catalysts which are suitable for the preparation of the alkanol-polyalkoxylate compounds according to the invention are known to the person skilled in the art, e.g. B. from the EP-A-0 654 302 . EP-A-0 700 949 EP-A-0 743 093 . EP-A-0 755 716 . EP-A-0 862 947 , WO 97/40086, WO 98/16310, WO 99/16775, WO 00/14045, WO 00/74843 and WO 00/74845. These documents are expressly and fully referred to.

For example, multimetal cyanide catalysts containing a multimetal cyanide complex compound of the general formula IV are suitable M ¹ _a [M ² (CN) _b (A) _c ] _d · fM ¹ _g X _n · h (H ₂ O) · eL (IV) in the
M ¹ at least one metal ion selected from the group consisting of Zn ²⁺ , Fe ²⁺ , Co ³⁺ , Ni ²⁺ , Mn ²⁺ , Co ²⁺ , Sn ²⁺ , Pb ²⁺ , Mo ⁴⁺ , Mo ⁶⁺ , Al ³⁺ , V ⁴⁺ , V ⁵⁺ , Sr ²⁺ , W ⁴⁺ , W ⁶⁺ , Cr ²⁺ , Cr ³⁺ , Cd ²⁺ ,
M ² at least one metal ion selected from the group consisting of Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Mn ²⁺ , Mn ³⁺ , V ⁴⁺ , V ⁵⁺ , Cr ²⁺ , Cr ³⁺ , Rh ³⁺ , Ru ²⁺ , Ir ³⁺
where M ¹ and M ^{2 are the} same or different,
A is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate or nitrate,
X is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate or nitrate,
and
L is a water-miscible ligand selected from the group consisting of alcohols, aldehydes, ketones, ethers, polyethers, esters, ureas, amides, nitriles and sulfides,
where a, b, c, d, g and n are selected so that the electroneutrality of the compound is ensured,
e is the coordination number of the ligand,
f is a fractional or whole number greater than 0 or 0 and
h a fractional or whole number greater than 0 or 0
mean.

• – M¹ steht für Zn²⁺
• – M² steht für Co³⁺ und/oder Fe³⁺
• – A steht für CN^–
• – L steht für tert.-Butanol
• – h oder e können gleich 0 sein.

Preferred multimetal cyanide catalysts of the formula IV are those which have one or more of the following features:

• - M ¹ stands for Zn ²⁺
• - M ² stands for Co ³⁺ and / or Fe ³⁺
• - A stands for CN ^-
• - L stands for tert-butanol
• - h or e can be 0.

Preferably are the multimetal cyanide complex compounds of the formula IV firm, inert, non-foamed carrier applied or introduced into it or shaped into shaped bodies.

method for the preparation of multimetal cyanide complex compounds of the formula Catalysts containing IV are known to the person skilled in the art, for example from WO 00/14045, the contents of which are hereby fully referred to is taken.

• a) Hinzufügen einer wässrigen Lösung eines wasserlöslichen Metallsalzes der allgemeinen Formel M¹ _m(X)_n, wobei M¹ mindestens ein Metallion, ausgewählt aus der Gruppe, enthaltend Zn²⁺, Fe²⁺, Co³⁺, Ni²⁺, Mn²⁺, Co²⁺, Sn²⁺, Pb²⁺, Fe³⁺, Mo⁴⁺, Mo⁶⁺, Al³⁺, V⁵⁺, Sr²⁺, W⁴⁺, W⁶⁺, Cu²⁺, Cr²⁺, Cr³⁺, Cd²⁺, Hg²⁺, Pd²⁺, Pt²⁺, V²⁺, Mg²⁺, Ca²⁺, Ba²⁺ und Mischungen daraus, X mindestens ein Anion, ausgewählt aus der Gruppe, enthaltend Halogenid, Hydroxid, Sulfat, Carbonat, Cyanid, Thiocyanat, Isocyanat, Carboxylat, insbesondere Formiat, Ace tat, Propionat, Oxalat, Nitrat bedeuten und m und n ganze Zahlen sind, die den Wertigkeiten von M¹ und X genügen, zu einer wässrigen Lösung einer Cyanometallat-Verbindung der allgemeinen Formel H_αM²(CN)_β(A)_ξ, wobei M² mindestens ein Metallion, ausgewählt aus der Gruppe, enthaltend Fe²⁺, Fe³⁺, Co³⁺, Cr³⁺, Mn²⁺, Mn³⁺, Rh³⁺, Ru²⁺, Ru³⁺, V⁴⁺, V⁵⁺, Co²⁺, Ir³⁺ und Cr²⁺ bedeutet und M² gleich oder verschieden M¹ sein kann, H Wasserstoff oder ein Metallion, üblicherweise ein Alkalimetall-, Erdalkalimetall- oder ein Ammoniumion bedeutet, A mindestens ein Anion, ausgewählt aus der Gruppe, enthaltend Halogenid, Hydroxid, Sulfat, Carbonat, Cyanat, Thiocyanat, Isocyanat, Carboxylat oder Nitrat, insbesondere Cyanid bedeutet, wobei A gleich oder verschieden X sein kann, und β eine ganze Zahl größer null und α und ξ ganze Zahlen größer oder gleich null sind, die so ausgewählt sind, dass die Elektroneutralität der Cyanidverbindung gewährleistet ist, wobei eine oder beide Lösungen gegebenenfalls mindestens einen wassermischbaren, Heteroatome enthaltenden Liganden enthalten können, der ausgewählt ist aus der Gruppe, enthaltend Alkohole, Ether, Ester, Ketone, Aldehyde Carbonsäuren, Amide, Sulfide oder Mischungen aus mindestens zwei der genannten Verbindungen, und mindestens eine der beiden Lösungen einen oberflächenaktiven Stoff enthält,
• b) gegebenenfalls Vereinigen der in Schritt a) gebildeten wässrigen Suspension mit einem wassermischbaren Heteroatome enthaltenden Liganden, ausgewählt aus der beschriebenen Gruppe, der gleich oder verschieden sein kann dem Liganden aus Schritt a),
• c) gegebenenfalls Abtrennen der Multimetallcyanidverbindung aus der Suspension.

Multimetal cyanide catalysts, which are produced in the presence of surface-active substances, are particularly suitable for the preparation of the alkanol-polyalkoxylate compounds according to the invention, for example by the following process steps:

• a) adding an aqueous solution of a water-soluble metal salt of the general formula M ¹ _m (X) _n , where M ^{1 contains} at least one metal ion selected from the group comprising Zn ²⁺ , Fe ²⁺ , Co ³⁺ , Ni ²⁺ , Mn ²⁺ , Co ²⁺ , Sn ²⁺ , Pb ²⁺ , Fe ³⁺ , Mo ⁴⁺ , Mo ⁶⁺ , Al ³⁺ , V ⁵⁺ , Sr ²⁺ , W ⁴⁺ , W ⁶⁺ , Cu ²⁺ , Cr ²⁺ , Cr ³⁺ , Cd ²⁺ , Hg ²⁺ , Pd ²⁺ , Pt ²⁺ , V ²⁺ , Mg ²⁺ , Ca ²⁺ , Ba ²⁺ and mixtures thereof, X at least one anion from the group containing halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, carboxylate, in particular formate, ace tat, propionate, oxalate, nitrate and m and n are integers which satisfy the values of M ¹ and X. to an aqueous solution of a cyanometalate compound of the general formula H _α M ² (CN) _β (A) _ξ , where M ^{2 contains} at least one metal ion selected from the group comprising Fe ²⁺ , Fe ³⁺ , Co ³⁺ , Cr ³⁺ , Mn ²⁺ , Mn ³⁺ , Rh ³⁺ , Ru ²⁺ , Ru ³⁺ , V ⁴⁺ , V ⁵⁺ , Co ²⁺ , Ir ³⁺ and Cr ²⁺ and M ^{2 may be} identical or different M ¹ , H is hydrogen or a metal ion, usually an alkali metal, alkaline earth metal or ammonium ion, A is at least one anion selected from the group containing halide, hydroxide, sulfate, carbonate, cyanate , Thiocyanate, isocyanate, carboxylate or nitrate, in particular cyanide, where A can be the same or different X, and β is an integer greater than zero and α and ξ are integers greater than or equal to zero, which are selected so that the electroneutrality of the Cyanide compound is guaranteed, where one or both solutions may optionally contain at least one water-miscible, heteroatom-containing ligand, which is selected from the group consisting of alcohols, ethers, esters, ketones, aldehydes carboxylic acids, amides, sulfides or mixtures of at least two of the compounds mentioned , and at least one of the two solutions contains a surfactant,
• b) optionally combining the aqueous suspension formed in step a) with a ligand containing water-miscible heteroatoms, selected from the group described, which may be the same or different from the ligand from step a),
• c) optionally separating the multimetal cyanide compound from the suspension.

The platy multimetal cyanide compounds thus obtained are preferably crystalline and can have a cubic, tetragonal, trigonal, orthorhombic, hexagonal, monoclinic or triclinic crystal system exhibit.

For the preparation of the multimetal cyanide compounds for the suspensions according to the invention are used, it is advantageous, but not necessary, to use cyanometallate acid as the cyanometalate compound, since this does not produce a salt as a by-product.

This are preferably usable cyanometalate hydrogen acids stable in aqueous solution and easy to handle. Their production can, for example, as in W. Klemm, W. Brandt, R. Hoppe, Z. Anorg. Gen. Chem. 308, 179 (1961) described, starting from the alkali metal cyanometalate via the silver cyanometalate Cyanometallic acid respectively. One more way consists of using an alkali or alkaline earth metal cyanometalate convert acidic ion exchanger into a cyanometalate hydrogen acid, as for example in F. Hein, H. Lilie, Z. Anorg. Gen. Chem. 270, 45 (1952), or A. Ludi, H.U. Güdel, V. Dvorak, Helv. Chim. Acta 50, 2035 (1967). Further possibilities for the synthesis of the cyanometalate hydrogen acids can be found, for example in "Manual of the preparative Inorganic Chemistry ", G. Bauer (Editor), Ferdinand Enke Verlag, Stuttgart, 1981. For one The technical production of these compounds is the synthesis via ion exchangers the most beneficial way.

The Proportion of acid in the solution should be greater than 80% by weight, preferably greater than 90% by weight, in particular greater than 95% by weight, based on the total mass of cyanometalate complexes.

As Ligands containing heteroatoms become the organic ones described above Substances used. In a preferred embodiment of the manufacturing process will be the solutions in step a) no ligand containing heteroatoms is added, and also step b), adding from ligand containing heteroatoms to the precipitation suspension is omitted. It’s just, as mentioned above, at least one surface-active compound one or two solutions added in step a).

The to be used in the production of the multimetal cyanide catalysts surfactants Connections can anionic, cationic, nonionic and / or polymeric surfactants his.

In particular nonionic and / or polymeric surfactants are used. From this Group selected in particular, fatty alcohol alkoxylates, block copolymers are different Epoxies with different hydrophilicity, castor oil alkoxylates or block copolymers of epoxides and other monomers, such as acrylic acid or Methacrylic acid.

preferred Fatty alcohol alkoxylates are based on a fatty alcohol with 8 to 36 Carbon atoms, especially with 10 to 18 carbon atoms. This is preferably with ethylene oxide, propylene oxide and / or butylene oxide alkoxylated. The polyether part of the fatty alcohol alkoxylate according to the invention can thereby from pure ethylene oxide, propylene oxide or butylene oxide polyethers consist. Furthermore, copolymers of two are also used as the polyether part or three different alkylene oxides possible or block copolymers from two or three different alkylene oxides. The polyether part consists preferably of 2 to 50, in particular 3 to 15 alkylene oxide units.

As Surfactants are also pure polyether compounds or polyalkylene oxides suitable, in particular block copolymers of two or more alkylene oxides. Such block copolymers generally contain two or more, preferably two different polyether blocks, which differ in their hydrophilicity distinguish, for example one from ethylene oxide and one from Propylene oxide. The water solubility is about the lengths of the different blocks controlled. The molecular weights of such block copolymers are preferably in Range from 500 Da to 20,000 Da, particularly preferably 1000 Da to 6000 Da and especially at 1500 to 4000 Da. In the case of ethylene / propylene copolymers is Ethylene oxide content preferably 5 to 50 wt .-% and the propylene oxide Share preferably 50 to 95 wt .-%.

As Surfactants also come from copolymers or block copolymers of alkylene oxides, preferably ethylene oxide, with other monomers such as butyl methacrylate, Methyl methacrylate or methacrylic acid into consideration.

The surfactants Substances are usually already in at least one of the two solutions submitted. The surface-active substances are preferred in the solution given that in the precipitation is presented. The proportion of surfactant in the reaction mixture is preferably 0.01 to 70 wt .-%, particularly preferably 0.1 to 50 wt .-%, whole particularly preferably 0.2 to 40% by weight and in particular 0.5 to 30 % By weight, based on the total mass of those used in the production two solutions.

To produce the preferably crystalline multimetal cyanide compounds, an aqueous solution of a cyanometalate hydrogen acid or a cyanometalate salt is combined with the aqueous solution of a metal salt of the general formula M ¹ _m (X) _n . This is preferably done with a stoichiometry worked excess of the metal salt. It is particularly preferred to work with a molar ratio of the metal ion to the cyanometalate component of 1.1 to 7.0, preferably 1.2 to 5.0 and particularly preferably 1.3 to 3.0. In many cases it may be advantageous to submit the metal salt solution and add the cyanometalate compound, but the procedure can also be reversed. Thorough mixing, for example by stirring, is advantageous during and after the combination of the educt solutions.

The Content of cyanometalate compound in the cyanometalate reactant solution is based on the mass of cyanometalate reactant solution, preferably 0.1 to 30% by weight, preferably 0.1 to 20% by weight and in particular 0.2 to 10% by weight. The content of the metal salt component in the metal salt solution is preferably 0.1 to 50% by weight, particularly preferably 0.2 to 40% by weight and in particular 0.5 to 30 wt .-%, based on the mass of metal salt solution.

The Ligands containing heteroatoms are preferred after union of the two educt solutions added to the resulting suspension, with thorough mixing to watch out for. However, it is also possible to use the ligands entirely or partially add one of the two educt solutions. there one should, because of the change the salt solubility, the ligand, preferably the solution add to the cyanometalate compound.

The multimetal cyanide compounds produced by precipitation by the process described above can then by filtration or centrifugation of the liquid components of the precipitation suspension be separated. Different cleaning steps can separate subsequently, z. B. Wash with water or other suitable solvents. Subsequently the multimetal cyanide compound can be dried, e.g. B. at Temperatures of 30 ° C up to 180 ° C and press from 0.001 bar to 2 bar, preferably at temperatures between 30 ° C and 100 ° C and pressures of 0.01 bar to 1 bar.

The Use of the multimetal cyanide catalysts in the production of the polyether compounds according to the invention leads to a high turnover, usually greater than 90%, preferably greater than 95% and in particular larger than 98%, even with a high proportion of alkylene oxides of the formula I. In addition, the Use of these catalysts for advantageous molecular weight distributions and and thus to advantageous viscosity properties of the polyether compounds according to the invention at.

The Multimetal cyanide catalysts are preferably used in an amount from 0.001 to 5% by weight, particularly preferably 0.1 to 2% by weight and in particular 0.3 to 1 wt .-%, based on the amount of all used Alkylene oxides used.

Typical reaction temperatures for the reaction of the alcohols R ⁶ -OH with alkylene oxides are 70 to 200 ° C., preferably 80 to 180 ° C. and particularly preferably 90 to 150 ° C. The pressure is usually 0.1 to 30 bar, preferably 0.2 to 20 bar and in particular 0.5 to 15 bar. The reaction is usually carried out with the substantial exclusion of oxygen, e.g. B. under inert gases such as nitrogen or argon. As usual, the reaction product can be worked up by degassing volatile constituents in vacuo and, if appropriate, by filtration.

The Reaction of the alcohols with alkylene oxides can be carried out in a continuous Process or in a batch or semi-batch process. Because of the easier feasibility and the lower equipment costs, batch and semi-batch processes are preferred.

In many cases it is advantageous to react the alcohols with alkylene oxides in a semi-batch process. Using semi-batch processes is to be understood in the context of this invention, a method in which usually only a subset of the alkylene oxides to be converted less than 50% by weight, preferably less than 30% by weight and in particular less than 15% by weight directly with catalyst and starter (i.e. Alcohol) is added at the start of the reaction and the rest Subset over a period is added. The period of addition is in the Usually at least one sixth, preferably at least one fifth, especially preferably at least one third of the total reaction time. The total response time is dependent of and the reaction temperature is usually in the range of about 10 Minutes to 10 hours, such as 30 minutes to 7 hours.

The OH-terminated polyether compounds resulting from the process according to the invention, for example compounds of the formula III in which X represents OH, can subsequently be converted into amino- or polyamino-terminated compounds, for example compounds of the formula III in which X represents NR ⁷ R ⁸ , wherein the radicals R ⁷ and R ^{8 are} as defined above. These conversion reactions who hereinafter referred to as amino functionalizations. Examples of such processes for amino functionalization are the nucleophilic substitution of the terminal OH group by ammonia, primary or secondary amines, if appropriate after conversion of the OH group into a better leaving group, the reductive amination of the terminal OH group and the reaction of the terminal OH group. Group or a primary amino group introduced by the methods described above (X = NR ⁷ R ⁸ with R ⁷ = R ⁸ = H) with reactive cyclic amines, such as alky lenimines, for. B. ethyleneimine, with ring opening of the cyclic amines. In the context of this invention, the amino functionalization by reductive amination is preferred.

at the reductive amination, the polyether compounds with terminal OH group (X = OH) mixed with an amine and reduce under Conditions, usually in the presence of a catalyst, implemented. As Reducing agents are particularly suitable for hydrogen. As Catalysts come from copper, nickel, cobalt, iron or else Platinum or palladium catalysts, as is customary for hydrogenation reactions be used. Palladium-activated carbon is preferably used as the catalyst, Raney nickel or Raney copper are used. Particularly preferred as Catalyst are Ni contacts, i. H. Nickel on inorganic substrates. Ammonia, primary, come as amines Amines and secondary Amines and oligo- and polyamines, which are at least one primary and / or secondary Have amino group into consideration.

Examples of such amines are compounds of the formula HNR ⁷ R ⁸ , in which the radicals R ⁷ and R ^{8 are} selected from hydrogen, C ₁ -C ₂₀ alkyl, C ₃ -C ₈ cycloalkyl and C ₁ -C ₂₀ - Alkoxy radicals which can be interrupted and / or substituted by heteroatoms selected from N and O, the heteroatoms in turn being able to carry substituents, preferably selected from H, C ₁ -C ₆ alkyl, aryl and heteroaryl; or R ⁷ and R ⁸ together with the N atom to which they are attached form a 5- to 8-membered cycle which has one or two further heteroatoms selected from N and O and with one, two or three C. ₁ -C ₆ alkyl radicals can be substituted. Furthermore, R ⁷ and R ^{8 can} also represent C ₆ -C ₁₀ aryl and heteroaryl radicals. The aryl and heteroaryl radicals optionally have one to three substituents, selected for. B. under hydroxy and the aforementioned alkyl, cycloalkyl or alkoxy radicals and polyisobutene radicals.

Suitable radicals R ⁷ , R ⁸ are, for example, hydrogen, methyl, ethyl, n-propyl, sec-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl and n- Hexyl, 5-, 6- and 7-membered saturated, unsaturated or aromatic carbocycles and heterocycles, such as cyclopentyl, cyclohexyl, phenyl, toloyl, xylyl, cycloheptanyl, naphthyl, tetrahydrofuranyl, tetrahydropyranyl, dioxanyl, pyrrolidyl, pyrididyl, piperidyl.

Examples of compounds of the formula HNR ⁷ R ⁸ which have only a primary amino function are, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, hexylamine , Cyclopentylamine, cyclohexylamine, aniline and benzylamine.

Examples of compounds of the formula HNR ⁷ R ⁸ which have only a primary amino function and in which the radical R ⁷ or R ^{8 are} alkyl radicals which are interrupted and / or substituted by the heteroatom 0 are, for example, CH ₃ -OC ₂ H ₄ -NH ₂ , C ₂ H ₅ (-OC ₂ H ₄ -NH ₂ , CH ₃ -OC ₃ H ₆ (-NH ₂ , C ₂ H ₅ -OC ₃ H ₆ -NH ₂ , nC ₄ H ₉ -OC ₄ H ₈ -NH ₂ , HO-C ₂ H ₄ -NH ₂ , HO-C ₃ H ₇ -NH ₂ and HO-C ₄ H ₈ -NH ₂ .

Examples of compounds of the formula HNR ⁷ R ⁸ which have only a secondary amino function are, for example, dimethylamine, diethylamine, methylethylamine, di-n-propylamine, diisopropylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, dipentylamine, Dihexylamine, dicyclopentylamine, dicyclohexylamine and diphenylamine.

Examples of compounds of the formula HNR ⁷ R ⁸ which have only a secondary amino function and in which the radicals R ⁷ and R ^{8 are} alkyl radicals which are interrupted and / or substituted by the heteroatom O are, for example (CH ₃ -OC ₂ H ₄ ) ₂ NH, (C ₂ H ₅ -OC ₂ H ₄ ) ₂ NH, (CH ₃ -OC ₃ H ₆ ) ₂ NH, (C ₂ H ₅ (-OC ₃ H ₆ ) ₂ NH, (nC ₄ H ₉ - OC ₄ H ₈ ) ₂ NH, (HO-C ₂ H ₄ ) ₂ NH, (HO-C ₃ H ₆ ) ₂ NH and (HO-C ₄ H ₈ ) ₂ NH.

Examples of compounds of the formula HNR ⁷ R ⁸ in which R ⁷ and R ⁸ together with the N atom to which they are attached form a 5-, 6- or 7-membered cycle, the one or two hetroatomas selected from N and O, and can be substituted with one, two or three C ₁ -C ₆ alkyl radicals are, for example, pyrrolidine, piperidine, morpholine and piperazine and their substituted derivatives, such as NC ₁ -C ₆ alkyl piperazines and dimethylmorpholine.

Examples of compounds of the formula HNR ⁷ Re ⁸ which have N-interrupted and / or substituted alkyl radicals are alkylenediamines, dialkylenetriamines, trialkylenetetramines, tetraalkylenepentaamines and Polyalkylene polyamines with a degree of polymerization of 5 to 100, such as oligo- or polyalkyleneimines, in particular oligo- or polyethyleneimines, preferably oligoethyleneimines, consisting of 2 to 20, preferably 2 to 10 and particularly preferably 2 to 6 ethyleneimine units. Suitable such compounds are in particular ethylenediamine, n-propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and the above-mentioned polyethyleneimines, and also their alkylation products which have at least one primary or secondary amino function, e.g. B. 3- (Dimethylamino) -n-propylamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine and N, N, N ', N'-tetramethyldiethylenetriamine. Ethylene diamine is also suitable.

Further examples of compounds of the formula HNR ⁷ R ⁸ are the reaction products of alkylene oxides, in particular ethylene oxide, with primary amines, and copolymers of ethylene oxide with ethylene imine and / or primary or secondary C ₁ -C ₆ -alkylamines.

Preferred compounds of the formula HNR ⁷ R ⁸ are 3- (dimethylamino) -n-propylamine, di [3- (dimethylamino) -n-propyl] amine, di [3- (diethylamino) -n-propyl] amine, di [2 - (dimethylamino) ethyl] amine, ammonia, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, dicyclohexylamine, pyrrolidine, piperidine, morpholine, dimethylmorpholine, N-methylpiperazine, HO-C ₂ H ₄ -NH ₂ , (HO-C ₂ H ₄ ) ₂ NH, H ₃ CO- (CH ₂ ) ₂ -NH ₂ , H ₃ CO- (CH ₂ ) ₃ -NH ₂ , diethylenetriamine, triethylenetetramine, N, N-diethylethylenediamine, N, N, N ', N'-tetramethyldiethylene triamine, tetraethylene pentamine and polyethyleneimines with an average degree of polymerization in the range from 6 to 10.

Particularly preferred compounds of the formula HNR ⁷ R ⁸ are 3- (dimethylamino) -n-propylamine, di [3- (dimethylamino) -n-propyl] amine, dimethylamine, diethylamine, tetraethylene pentamine and morpholine.

The Reductive amination is usually carried out at a temperature in the range from about 50 to 300 ° C, preferred 80 to 200 ° C, carried out. The reductive amination is preferably at a pressure in the range from 50 to 500 bar, preferably 80 to 300 bar.

In the case of reductive amination, it may be expedient to use a suitable solvent which is inert under the reaction conditions in order to reduce the viscosity of the reaction mixture. Less polar solvents, such as aliphatic, cycloaliphatic and aromatic hydrocarbons, are suitable as solvents. These hydrocarbons should preferably be low in sulfur. Suitable hydrocarbons are e.g. B. linear or branched C ₅ -C ₁₆ alkanes and in particular dodecane, 2,4,4-trimethylpentane, and cyclohexane and toluene.

The polyethers contained in the polyether compositions obtained by the process according to the invention preferably have a weight-average molecular weight M _w of at least 450 g / mol, particularly preferably of at least 550 g / mol and in particular of at least 600 g / mol. The weight-average molecular weight is preferably at most 3500 g / mol, particularly preferably at most 2500 g / mol. As a rule, the weight-average molecular weight that is optimal for the application properties is lower, the higher the proportion of incorporated alkylene oxides of the formula I. This applies in particular to alkylene oxides of the formula I with R ¹ and R ² = CH ₃ and R ³ and R ⁴ = H.

The viscosity of the polyether compositions according to the invention is 40 ° C, preferably in the range from 30 to 500 mPa · s, particularly preferably from 50 to 300 mPa · s.

The polyether compositions obtained by the process according to the invention advantageously advantageously contain a significant proportion of unsaturated components. These can result, for example, from rearrangement of alkylene oxides to allyl compounds and subsequent alkoxylation of these allyl compounds. Furthermore, unsaturated components can also arise during the cleavage of polyether chains in the course of the process. Preferably, the polyether compositions obtained by the inventive process have an iodine number determined according to Hanus is from 1 to 20, particularly preferably 3 to 18 g of I _2/100 g polyether. In general, using alkylene oxide mixtures of 1-butene oxide with isobutene oxide and / or 2,3-butene oxide results in higher proportions of unsaturated components than in the homopolymerization of 1-butene oxide.

Preferably have the polyether compositions obtained by the process according to the invention a residual content of monohydroxy compounds used as starters of at most 5% by weight, particularly preferably at most 1% by weight and in particular at most 0.2% by weight, based on the amount originally used. In particular, the residual content of monohydroxy compounds is approximately 0% (i.e. below the detection limit).

The polydispersity (PD) of the polyether compositions obtained by the process according to the invention (ie the quotient of weight-average and number-average molecular weight M _w / M _n ) is preferably in a range from 1.03 to 1.70, particularly preferably 1.04 to 1.60 and especially from 1.05 to 1.50. The polydispersity can be determined by means of gel permeation chromatography (GPC).

On the invention further relates to those according to the process of the invention obtained polyether compositions.

The polyether compositions according to the invention, preferably those containing OH-terminated polyether compounds, in particular those of the formula III in which X is OH, are suitable are excellent as carrier oils for detergents and dispersants in fuel and lubricant compositions.

Especially they are preferred in fuel compositions, in particular in gasoline fuel compositions with direct injection performance, used.

object The present invention is therefore also the use of polyether compositions as carrier oils for detergents and dispersants in fuel and lubricant compositions.

The polyether compositions according to the invention, preferably those which contain amine- or polyamine-terminated polyether compounds, in particular those of the formula III in which X represents NR ⁷ R ⁸ , are outstandingly suitable as detergents and / or dispersants in fuel and lubricant compositions. They are particularly preferably used in fuel compositions, in particular in gasoline fuel compositions.

object The present invention is therefore also the use of polyether compositions as detergents and / or dispersants in fuel and lubricant compositions.

• (a) Polyisobutenamine, welche durch Hydroformylierung von hochreaktivem Polyisobuten und anschließende reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen wie Dimethylenaminopropylamin, Ethylendiamin, Diethylentriamin, Triethylentetramin oder Tetraethylenpentamin erhältlich sind, z. B. die in der EP-A 244 616 beschriebenen,
• (b) Poly(iso)butenamine, welche durch Chlorierung von Polybutenen oder Polyisobutenen mit Doppelbindungen überwiegend in der β- und γ-Position und anschließende Aminierung mit Ammoniak, Monoaminen oder den oben genannten Polyaminen erhältlich sind,
• (c) Poly(iso)butenamine, welche durch Oxidation von Doppelbindungen in Poly(iso)butenen mit Luft oder Ozon zu Carbonyl- oder Carboxylverbindungen und anschließende Aminierung unter reduzierenden (hydrierenden) Bedingungen erhältlich sind,
• (d) Polyisobutenamine, welche aus Polyisobutenepoxiden durch Umsetzung mit Aminen und nachfolgende Dehydratisierung und Reduktion der Aminoalkohole erhältlich sind, z. B. die in der DE-A 196 20 262 beschriebenen,
• (e) gegebenenfalls Hydroxylgruppen enthaltende Polyisobutenamine, welche durch Umsetzung von Polyisobutenen mit einem mittleren Polymerisationsgrad P = 5 bis 100 mit Stickoxiden oder Gemischen aus Stickoxiden und Sauerstoff und anschließende Hydrierung dieser Umsetzungsprodukte erhältlich sind, z. B. die in der WO-A 97/03946 beschriebenen,
• (f) Hydroxylgruppen enthaltende Polyisobutenamine, welche durch Umsetzung von Polyisobutenepoxiden mit Ammoniak, Monoaminen oder den oben genannten Polyaminen erhältlich sind, z. B. die in der EP-A 476 485 beschriebenen,
• (g) Polyetheramine, welche durch Umsetzung von C₂-C₃₀-Alkanolen, C₆-C₃₀-Alkandiolen, Mono- oder Di-C₂-C₃₀-Alkylaminen, C₁-C₃₀-Alkylcyclohexanolen oder C₁-C₃₀-Alkylphenolen mit 1 bis 30 Mol Ethylenoxid und/oder Propylenoxid und/oder Butylenoxid pro Hydroxyl- bzw. Aminogruppe und anschließende reduktive Aminierung mit Ammoniak, Monoaminen oder den oben genannten Polyaminen erhältlich sind, auch Polyetheramine mit Carbamat-Struktur sind verwendbar,
• (h) "Polyisobuten-Mannichbasen", welche durch Umsetzung von Polyisobuten-substituierten Phenolen mit Aldehyden und Monoaminen oder den oben genannten Polyaminen erhältlich sind, z. B. die in der EP-A 831 141 beschriebenen.

Typical detergents and / or dispersants which are known from the prior art are, for example:

• (a) Polyisobutenamines, which are obtainable by hydroformylation of highly reactive polyisobutene and subsequent reductive amination with ammonia, monoamines or polyamines such as dimethyleneaminopropylamine, ethylene diamine, diethylene triamine, triethylene tetramine or tetraethylene pentamine, e.g. B. in the EP-A 244 616 described,
• (b) poly (iso) butenamines, which are obtainable by chlorination of polybutenes or polyisobutenes with double bonds predominantly in the β and γ position and subsequent amination with ammonia, monoamines or the above-mentioned polyamines,
• (c) poly (iso) butenamines which can be obtained by oxidation of double bonds in poly (iso) butenes with air or ozone to give carbonyl or carboxyl compounds and subsequent amination under reducing (hydrogenating) conditions,
• (d) Polyisobutenamines, which are obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, e.g. B. in the DE-A 196 20 262 described,
• (e) optionally hydroxyl-containing polyisobutenamines, which are obtainable by reacting polyisobutenes with an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen and subsequent hydrogenation of these reaction products, for. B. those described in WO-A 97/03946,
• (f) Polyisobutenamines containing hydroxyl groups, which are obtainable by reacting polyisobutene epoxides with ammonia, monoamines or the above-mentioned polyamines, e.g. B. in the EP-A 476 485 described,
• (g) polyetheramines which are obtained by reacting C ₂ -C ₃₀ alkanols, C ₆ -C ₃₀ alkanediols, mono- or di-C ₂ -C ₃₀ alkylamines, C ₁ -C ₃₀ alkylcyclohexanols or C ₁ -C ₃₀ alkylphenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl or amino group and subsequent reductive amination with ammonia, monoamines or the above-mentioned polyamines are also available, polyetheramines with a carbamate structure can also be used,
• (h) "Polyisobutene Mannich bases" which can be obtained by reacting polyisobutene-substituted phenols with aldehydes and monoamines or the above-mentioned polyamines, e.g. B. in the EP-A 831 141 . described

Common dispersants Examples are imides, amides, esters and ammonium and alkali metal salts of polyisobutenesuccinic anhydrides, which are used in particular in lubricating oils, but sometimes also used as detergents in fuel compositions.

Other gasoline additives that can be used to prevent valve seat wear can be used together with the polyether compounds according to the invention; Here, for example, carboxyl groups or additives containing their alkali metal or alkaline earth metal salts, such as, for example, copolymers of C ₂ -C ₄₀ olefins with maleic anhydride with a total molecular weight of 500 to 20,000, their carboxyl groups wholly or partly to the alkali metal or alkaline earth metal salts and a remainder the carboxyl groups are reacted with alcohols or amines, as in the EP-A 307 815 are described, or sulfonic acid groups or additives containing their alkali metal or alkaline earth metal salts such as, for example, alkali metal or alkaline earth metal salts of alkyl sulfosuccinic acid esters, as described in US Pat EP-A 639 632 are of interest. Valve seat wear-inhibiting gasoline fuel additives of this type can advantageously also be used in combination with conventional fuel detergents such as poly (iso) butenamines, their hydrogenation products or polyetheramines, as described in WO-A 87/01126.

object The present invention also includes fuel and lubricant additive concentrates, which are the polyether compositions of the invention in amounts of 0.1 to 80, in particular 0.5 to 60% by weight on the total amount of concentrates. These concentrates usually contain also those listed above Detergents or dispersants as well as other components and Tools and solutions or diluent, z. B. aliphatic and aromatic hydrocarbons such as solvent Naphtha.

Other common components and auxiliaries are corrosion inhibitors, for example based of ammonium salts of organic carboxylic acids or film of heterocyclic aromatics in non-ferrous metal protection, antioxidants or stabilizers, for example based on amines such as p-phenylenediamine, Dicyclohexylamine or derivatives thereof or of phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, demulsifiers, antistatic agents, Metallocenes such as ferrocene or methylcyclopentadienylmanganese tricarbonyl, lubricity (Lubricity additives) such as certain fatty acids, alkenyl succinic acid esters, Bis (hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil as well Dyes (markers). Sometimes amines are also used to lower the pH value of the fuel added.

Other suitable components and additives are conventional carrier oils, for example mineral carrier oils (base oils), in particular those of the viscosity class "Solvent Neutral (SN) 500 to 2000", and synthetic carrier oils based on olefin polymers with M _N = 400 to 1800, especially on polybutene - or polyisobutene-based (hydrogenated or non-hydrogenated), and based on polyalphaolefins or polyinternal olefins.

object The present invention further includes fuel and lubricant compositions, in particular Fuel compositions, especially petrol compositions, which are the polyether compositions of the invention contained in effective amounts. Effective amounts are in the Usually in fuel compositions 10 to 5000 ppm by weight, preferred 30 to 3500 ppm by weight and in particular 50 to 1000 ppm by weight and at Lubricant compositions 0.1 to 10% by weight, in particular 0.5 up to 5% by weight, based in each case on the total amount of the composition, to understand. The fuel and lubricant compositions usually contain the compounds of the invention as carrier oils as well those listed above Detergents or dispersants as well as the other usual ones mentioned for this Components and auxiliaries as well as solvents or diluents.

The fuel compositions according to the invention can also as combinations of petrol with a mixture from polyether compounds, polyisobutenamine detergents, in particular those of the aforementioned groups (a), (b), (c) or (d), and corrosion inhibitors and / or lubricity improvers based on carboxylic acids or fatty acids, which can exist as monomeric and / or dimeric species.

The polyether compounds according to the invention are able to avoid the undesired "valve plugging" in particular Avoid gasoline engines effectively. They are still usually sufficiently compatible with the other additives so that no segregation effects occur. Their viscosity behavior also does not cause formulation problems.

The primarily used as carrier oils OH-terminated polyether compounds also show effect as Detergents. They therefore achieve one even with low doses high contribution to the overall performance of an additive package or one Fuel or Lubricant composition with regard to detergent action and enable therefore at least a partial saving of the more expensive detergents. Those primarily used as detergents and / or dispersants amino-terminated polyether compounds show good compatibility with carrier oils, in particular with the above, good effectiveness, in particular with regard to the prevention and removal of deposits in internal combustion engines, and are also characterized by an advantageous viscosity behavior out.

The polydispersities were determined by GPC. The calibration was carried out with polystyrene. The internal standard was toluene, solvent tetrahydrofuran. The flow was 1 ml / min. The following columns were used: guard column: PSS, SDV 8 × 50 mm, 5 μ; Separation columns: SDV 100 Å, 10 ³ Å, 10 ⁵ Å, every 8 × 300 mm, 5 μ. The detection was carried out using RI detectors.

General manufacturing instructions A for polyether compounds according to the invention:

In a steel autoclave with a usable volume of 250 ml a mixture consisting of tridekanol N (alcohol mixture of trimerized Butene) as a starter and the catalyst DMC GrG494K submitted. To closing of the autoclave, the reaction mixture is homogenized by stirring using a magnetic stirrer.

To remove residual water, the reaction mixture is heated to 100 ° C. and evacuated to a pressure of less than 5 mbar for 2 hours. Subsequently, the autoclave was charged with N ₂ and is filled bar absolute purged three times with N ₂ at a pressure of. 4 The reactor is then completely depressurized to a pressure of 1.5 bar and the respective reaction temperature is set. The alkylene oxides are added via a storage vessel.

To The corresponding temperature is reached in the autoclave The amount of alkylene oxide added in a controlled manner. For security reasons wait after adding a first small amount of alkylene oxide, whether the reaction has started. The onset of the reaction is through changes of pressure and / or temperature is detected. If the reaction has used recognizable, the remaining amount of alkylene oxide within of the specified periods added. The temperature and pressure curve are measured and recorded.

To Completion of the alkylene oxide addition becomes a post-reaction time of Adhered to for 1 hour. Then the autoclave is relaxed and for 15 minutes evacuated (less than or equal to 5 mbar). Possibly not implemented Alkylene oxide is collected using a low-temperature cold trap. After this cooling down the autoclave is opened to about room temperature and the reaction product is Pressure filtration (depth filter with 5 μm) separated from the solid catalyst.

Example 1:

20 g of starter and 0.5 g of catalyst are placed in an autoclave. To start the reaction, 10 g of propylene oxide are added at 150 ° C. The rise in temperature and pressure proves the start of the reaction. Subsequently is a mixture within 60 minutes at 150 ° C in an autoclave metered in from 44.3 g of isobutylene oxide and 25.7 g of propylene oxide. To as described above, 98.2 g of a clear, slightly viscous liquid receive.

Example 2:

10 g of starter and 0.5 g of catalyst are placed in an autoclave. To start the reaction, 10 g of propylene oxide are added at 150 ° C. The rise in temperature and pressure proves the start of the reaction. Subsequently is a mixture within 60 minutes at 150 ° C in an autoclave metered in from 49.4 g of isobutylene oxide and 30.2 g of propylene oxide. To as described above, 99 g of a clear, light viscous liquid receive.

Example 3:

6.7 g of starter and 0.5 g of catalyst are placed in an autoclave. To start the reaction, 10 g of propylene oxide are added at 150 ° C. The rise in temperature and pressure proves the start of the reaction. Subsequently is a mixture within 60 minutes at 150 ° C in an autoclave metered in from 51.7 g of isobutylene oxide and 31.6 g of propylene oxide. To as described above, 99.1 g of a clear, slightly viscous liquid receive.

The The polyether compounds of Examples 4 to 9 were prepared analogous to Examples 1 to 3 according to the general rule A. The amounts of isobutene oxide and propene oxide were chosen as the calculated number average molecular weights required. The Results are shown in Table 1.

General manufacturing instructions B for polyether compounds according to the invention:

A mixture of tridecanol N and the catalyst DMC GrG494K is placed in a 250 ml three-necked flask with reflux condenser, inert gas connection (N ₂ ) and storage vessel for the alkylene oxides. To remove residual water, depending on the type of starting materials, the reaction mixture is generally heated to about 100 ° C. and evacuated for 2 hours to a pressure of less than 5 mbar. The flask with N ₂ is gassed and purged three times with N _2. The subsequent reaction was carried out under a nitrogen atmosphere. The alkylene oxides were added via the storage vessel.

To The corresponding temperature is reached in the three-necked flask The amount of alkylene oxide added in a controlled manner. For security reasons wait after adding a first small amount of alkylene oxide, whether the reaction has started. The onset of the reaction is through changes of pressure and / or temperature is detected. If the reaction has used recognizable, the remaining amount of alkylene oxide within of the specified periods dosed so that the reaction mixture under slight reflux remains at the boil.

To Completion of the alkylene oxide feed becomes a post-reaction time of Adhered to for 1 hour. After that, the glass apparatus is removed unreacted monomers evacuated. Possibly not implemented Alkylene oxide is collected using a low-temperature cold trap. After this cooling down the reaction product is over a pressure filtration (depth filter with 5 μm) separated from the solid catalyst.

Example 10:

20 g of starter and 0.5 g of catalyst are placed in a three-necked flask. To start the reaction, 10 g of a mixture of equimolar Amounts of isobutylene oxide and 1,2-butylene oxide were added at 90 ° C. The increase in condensate at the reflux condenser is documented the start of the reaction. Then within 60 Minutes at 90 ° C 80 g of the equimolar Mixture (isobutylene oxide / 1,2-butylene oxide) metered in. Like above Working up described 97.8 g of a clear, slightly viscous liquid receive.

The The polyether compounds of Examples 11 to 15 were prepared analogous to Example 10 according to general rule B. The amounts of isobutene oxide and butene oxide were chosen as the calculated number average Molecular weights required it. The results are in the table 1 reproduced. The polyether composition obtained in Example 13 contained 4.7 mmol / kg unsaturated Ingredients. The Hanus iodine number was 12 g iodine / 100 g. The OH number was 74 mg KOH / g. The polydispersity was 1.21.

Example 16:

Example 16 was carried out analogously to Example 11, but instead of the equimolar mixture of isobutylene oxide and 1,2-butylene oxide, a mixture of alkylene oxides was used which was obtained by oxidation or epoxidation of raffinate I and had the following composition: isobutane: 3.4 mol% n-butane: 7.4 mol% 1,2-butene: 29.9 mol% 2,3-trans-butene: 7.9 mol% 2,3-cis-butene: 4.6 mol% isobutene: 46.8 mol%

Example 17:

Example 17 was carried out analogously to Example 11, but instead of the equimolar mixture of isobutylene oxide and 1,2-butylene oxide, a mixture of alkylene oxides was used which was obtained by oxidation or epoxidation of raffinate II and had the following composition: isobutane: 6.2 mol% n-butane: 13.3 mol% 1,2-butene: 55.6 mol% 2,3-trans-butene: 14.6 mol% 2,3-cis-butene: 8.5 mol% isobutene: 1.8 mol%

General working instructions C (polyetheramines):

The produced according to the invention OH-terminated polyether compounds can be used without further pretreatment a reductive amination with ammonia or a primary or secondary Be subjected to amine. If the alkoxylates have a higher viscosity, it may be advantageous to use a suitable inert solvent, for example branched aliphatic hydrocarbons such as Isododecane, so dilute that a viscosity the solution from 50 to 200 mm2 / s at 20 ° C results.

ammonia or amine are usually in excess, based on the Alkoxylate used, e.g. B. in 2 to 100 times, preferably 10- to 80-fold molar excess with ammonia and 1.5 to 50-fold, preferably 2 to 20-fold excess in primary or secondary Amines.

The Mixture of alkoxylate and amine is commercially available in the presence of a available Hydrogenation catalyst such as Raney nickel, Raney cobalt or one Nickel contact, at elevated Pressure, e.g. B. in the range of 10 to 300 bar, preferably 50 to 250 bar, in a pressure reactor, e.g. B. a rolling autoclave, at increased Temperatures, e.g. B. 80 to 300 ° C, preferably 20 to 250 ° C, treated with hydrogen. After cooling, the catalyst is separated by filtration, removes excess amine, z. B. by distillation in vacuo, and distilled if necessary Editorial water still contained azeotropically or under an inert gas stream from.

Example 18

500 g of the polyether compound obtained according to Example 11 were, without further purification and without the addition of a solvent, in a roller autoclave in the presence of 100 g of nickel on ZrO ₂ as a catalyst at a pressure of 200 bar and a temperature of 100 ° C with 400 g of ammonia (43 , 3-fold molar excess) implemented. The pressure is set with H ₂ . The reaction time was 20 minutes. After cooling to room temperature, the catalyst was removed by filtration, the excess ammonia was removed in vacuo (less than 5 mbar) and the water of reaction was distilled off azeotropically. This gave 498 g of a clear liquid with a viscosity of 64 mm 2 / s at 40 ° C., which had an amine number of 57 mg KOH per g of polyetheramine.

application Technology investigations

Example 19

In A Mercedes Benz M 102 electric motor was tested in accordance with the CEC method F-05-A-93 performed for intake valve cleanliness. For this, it was initially a market standard Eurosuper base fuel according to EN 228 used, which contained no additives. It was in at the end of the test the sum over all inlet valves measured 368 mg deposits. Then was the test procedure with the same engine (with the 368 mg deposits) repeated, but here the same basic fuel was used according to EN 228 used with 300 mg of the polyetheramine obtained from Example 18 was displaced per kg of fuel. The deposits had settled at the end of the test decreased from 368 mg to 12 mg in total across all intake valves.

Example 20

Example 20 was carried out analogously to Example 19, but a commercially available Eurosuper base fuel according to EN 228 was used as the additive, which contains 200 mg of the polyether obtained from Example 14 and 100 mg of one per kg of base fuel as additives EP 244 616 , Example 1, obtained 3: 1 mixture of polyisobutenamine and polyisobutene. At the end of the test, the deposits had decreased from 368 mg to 4 mg in total across all inlet valves.

Example 21

Example 21 was carried out analogously to Example 19, but a commercially available Eurosuper base fuel according to EN 228 was used as the additive, which contains 200 mg of the polyether obtained from Example 14 and 100 mg of one according to WO 01/25295, Example 6 per kg of base fuel. obtained polyisobutene phenol Mannich adduct. At the end of the test, the deposits had decreased from 368 mg to 6 mg in total across all inlet valves. Table 1:

Claims (15)

Process for the preparation of a polyether composition, in which a monohydroxy compound with at least one alkylene oxide of the general formula I

wherein two of the radicals R ¹ to R ^{4 are} C ₁ -C ₆ alkyl and the rest are hydrogen or C ₁ -C ₆ alkyl, in the presence of a multimetal cyanide catalyst to obtain a polyether composition containing hydroxy-terminated polyether. The method of claim 1, wherein the obtained Polyether composition of an amino functionalization to obtain a polyether composition that is amino and / or polyamino terminated Contains polyether, subjects. Method according to one of the preceding claims, wherein the polyethers have at least 10 mole percent repeating units of alkylene oxides of the general formula I, based on the total proportion of ether repeat units, built-in included. Method according to one of the preceding claims, wherein the polyethers additionally contain repeating units of alkylene oxides, which are selected from compounds of the general formula II

wherein R ^{5 is} hydrogen or C ₁ -C ₆ alkyl. Method according to one of the preceding claims, wherein the alkylene oxides of the formula I are selected from cis-2,3-butene oxide, trans-2,3-butene oxide, 2-methyl-1,2-propene oxide and mixtures thereof. The method of claim 5, wherein the polyethers are at most 70 mol%, preferably at most 60 mol%, in particular at most 50 mol% repeat units of 2-methyl-1,2-propene oxide, based on the total proportion of ether repeat units contain. Method according to one of the preceding claims, wherein the polyether composition obtained has a viscosity in the range from 30 to 500 mPas, preferably 50 to 300 mPa · s, measured at 40 ° C. Method according to one of the preceding claims wherein the polyether composition obtained has an iodine number determined according to Hanus is from 1 to 20 g I _2/100 g polyether. Method according to one of the preceding claims, wherein the polyether composition obtained has a residual content of monohydroxy compound of at most 5 wt .-%, based on the amount used. Method according to one of the preceding claims, wherein the polyether composition obtained has a polydispersity (PD) in the Range from 1.03 to 1.70. Polyether composition obtainable by a process as in one of the claims 1 to 10 defined. Use of a polyether composition according to claim 11 as a carrier oil for detergents and dispersants in fuel and lubricant compositions. Use of a polyether composition according to claim 11 as a detergent and / or dispersant in fuel and lubricant compositions. Containing fuel and lubricant additive concentrates at least one polyether composition according to claim 11 in quantities from 0.1 to 80% by weight. Fuel and lubricant compositions containing a majority of a liquid carbon Hydrogen fuel or a liquid, semi-solid or solid lubricant and a detergent-active amount of at least one polyether composition according to claim 11.