Method of obtaining acylated alkoxylates of secondary alcohols and alkoxylates of secondary alcohols

FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining acylated alkoxylate of secondary alcohol of formula R1-C(O)-(OA)n-OR2(I), in which R1 is linear or branched alkyl group, including from 1 to 30 carbon atoms, optionally substituted cycloalkyl group, which includes from 5 to 30 carbon atoms, or optionally substituted aryl group, including from 6 to 30 carbon atoms, OA stands for one or several oxyalkylene fragments, which can be similar or different, n stands for integer number in the range from 0 to 70, and R2 is linear or branched alkyl group, including from 4 to 32 carbon atoms, optionally substituted cycloalkyl group, including from 5 to 32 carbon atoms, or optionally substituted bicycloalkyl group, including from 7 to 32 carbon atoms, where claimed method includes: (i) interaction of one or several olefins with internal double bond with one or several carboxylic acids in presence of catalytic composition with obtaining one or several ethers of carboxylic acid; (ii) interaction of one or several ethers of carboxylic acid, obtained at stage (i), with one or several alkylene oxide reagents in presence of catalytically efficient quantity of catalytic composition, which includes: (a) one or several salts of alkali earth metals and carboxylic acids and/or hydroxycarboxylic acids, which include 1-18 carbon atoms, and/or hydrates of the former; (b) oxygen-containing acid, selected from sulfuric acid and orthophosphoric acid; (c) alcohol, containing from 2 to 39 carbon atoms; and/or products of (a), (b) and/or (c) interactions with obtaining one or several acylated alkoxylates of secondary alcohols.

EFFECT: invention also relates to methods of obtaining alkoxylates of secondary alcohols and alkoxy sulfates of secondary alcohols, including the claimed method.

10 cl, 4 ex, 1 dwg, 1 tbl

 

The technical FIELD TO WHICH the INVENTION RELATES.

The present invention relates to a method for producing acylated alkoxylated secondary alcohols and alkoxylated secondary alcohols.

The LEVEL of TECHNOLOGY

A wide range of products which are applicable, for example, as a nonionic surfactant, wetting and emulsifying agents, solvents, and chemical intermediates, is obtained by addition reactions of (reactions alkoxysilane) alkalisation (epoxides) to organic compounds having one or more active hydrogen atoms.

For example, ethoxylates of alcohols can be obtained by the interaction of ethylene oxide with aliphatic alcohols comprising from 6 to 30 carbon atoms. Such ethoxylates and less relevant propoxylate, as well as compounds containing as oxyethylene and oxypropylene group, are widely used as nonionic detergent components in cleaning compositions and personal care products.

In the US 2008/0167215 A1 discloses certain acylated alkoxylated alcohols intended for use as a surfactant with low foaming.

The sulfated alkoxylated alcohols also have a wide range of applications, especially as anionic surfactants. Sulfated ethoxylates of higher secondary alcohols (SAES) in a wide range of applications is bespechivaet properties, comparable with the properties of anionic surfactants, such as linear alkylbenzenesulfonate and ethoxysulfuron primary alcohols, and sulfonates methyl esters. These substances can be used in the manufacture of household detergents including Laundry detergent, liquid Laundry detergent, liquid detergents for washing dishes and other household cleansers and emollients and compositions for personal hygiene, and, in addition, as a surfactant for (dilution) of the surface-active composition by water flooding of oil wells and as surface-active component, used, for example, in alkaline, surfactant and polymer-containing mixtures, suitable for improving oil recovery.

One of the typical ways of getting alkoxysilane alcohols, such as alkoxylated linear or branched primary alcohols, is hydroformylating olefins with getting oxaspiro and subsequent alkoxysilane obtained alcohol by reaction with a suitable alkalization, for example with ethylene oxide or propylene oxide. However, the methods comprising hydroformylating, are costly, and hydroformylation causes the formation of linear or branched primary alcohols (depending on the type of reaction get oxaspiro), which then must be alkoxycarbonyl.

For some applications the best result can provide a mixture of alkoxylated secondary alcohols (e.g., enhanced oil recovery (EOR), in connection with the ability to dissolve oil).

Alkoxylated secondary alcohols are usually obtained by oxidation/hydroxylation of paraffins, for example, by the reaction of Bashkirova, followed by alkoxysilanes.

However, the oxidation of paraffins to secondary alcohols and their subsequent alkoxysilane, as a rule, represents a complex two-stage process and, therefore, is expensive by synthesis.

This method includes obtaining secondary alcohols directly from paraffins by oxidation with the use of boric acid as a catalyst. Strictly speaking, the boron compound is not a catalyst, because it is consumed during the reaction. Its function is to protect the oxidation product (secondary alcohol) due to the formation of stable to oxidation of the ester of boric acid. In the whole process, including re-allocation of boric acid from the reaction mixture, boric acid really plays the role of "catalyst", as its second function is to increase the rate of oxidation. During the reaction are formed esters of boric acids and secondary alcohols, and can be separated from paraffin distillation, if the number of carbon atoms is (the number of carbon atoms in the carbon chain alcohol) alcohol is 14 or less. However, if the number of carbon atoms is 15 or more, required for the distillation temperature is the decomposition temperature of the ester of boric acid or exceeds it, and therefore, the usual method of distillation may be ineffective.

In addition, the oxidation of paraffins in the presence of derivatives of boric acid leads to the formation of diols as one of the main by-products (see N.Kurata and K.Koshida, Hydrocarbon Processing, 1978, 57(1), 145-151 and N.J.Stevens and J.R.Livingston, Chem.Eng.Progress, 1968, 64(7), 61-66). Thus, we should expect that only after a very thorough cleaning of the above mentioned pollutants diols secondary alcohols will be suitable for alkoxysilane and that the cost of such cleaning can make this method of synthesis in General unsuitable from an economic point of view.

An alternative way of getting alkoxylated secondary alcohols described in US 6 017 875 A, includes acid-catalyzed joining of oligoarticular to olefins with internal double bonds. However, this way is time-consuming, because it leads to the formation also dialkylamides of oligoarticular and oligomers of olefins with internal double bonds as by-products. Thus, this path is also expensive.

In the modern practice of industrial production of ethoxylates of secondary alcohols is raissadat expensive two-stage method. In the first stage to the secondary alcohol added two or three ethyleneoxide groups using an acid catalyst (Lewis acid), receiving primary hydroxyl-containing ethoxylate small molecular weight (low molecular weight). In the second stage, after removal of the acid catalyst (mainly by neutralization)reaction with ethoxylate low molecular weight (preferably in a mixture with a primary alcohol) enter the desired additional number of ethylenoxy fragments, using a basic catalyst such as potassium hydroxide. This two-stage method has the advantage that inevitably formed a by-product of amoxilonline under acid catalysis (Lewis) - 1,4-dioxane - can effectively remove instant evaporation or distillation after removal or neutralization of the acid catalyst from the intermediate ethoxylate low molecular weight, to becoming an intermediate product in the final product with the desired level of amoxilonline.

However, it would be desirable to develop a simple and economical way of obtaining alkoxylated secondary alcohols, is not associated with the formation of 1,4-dioxane and alkoxylated with a very broad distribution of molecular weight alkoxylated fragments.

In this regard, it should be noted that the reactions proceed in alkylenes the Dov, as is well known, produce a mixture of products with different alkoxylate groups, each with a different number of attached fragments accelerated (oxyalkylene adducts). The number of attached fragments is a factor, which in many ways defines the properties of molecules alkoxylates, and efforts are being made to harmonize the average number of attached fragments accelerated in the product and/or distribution of this number in different molecules of the product with the intended usage of the product.

In the technique reported mixtures of alkoxylated that quite a significant proportion of the molecules had a number attached fragment accelerated (n)within a relatively narrow range of values, as on the preferred products for use in some detergent compositions (GB-A-1462134; Research Disclosure No 194010). Furthermore, it is known that alkoxylate with a narrow range of values of n are especially valuable chemical intermediates in the synthesis of some carboxyethylidene alilovic polyesters (US-A-4098818) and some sulfates alilovic esters (GB-A-1553561).

Therefore, it would be useful to develop an alternative method of obtaining alkoxylated secondary alcohols and in particular alkoxylated alcohols with a narrow range so as not tol is to avoid the necessity of applying hydroformylation, but also to avoid the application as intermediate rather unstable secondary alcohols (which can turn into olefins with internal double bonds).

The INVENTION

In accordance with the above, the present invention relates to a method for producing acylated alkoxylated secondary alcohols, where the method includes:

(i) the interaction of one or more olefins with internal double bond (hereinafter for convenience referred to as "internal olefins") with one or more carboxylic acids in the presence of a catalytic composition with one or more esters of carboxylic acids;

(ii) the interaction of one or more esters of carboxylic acid, obtained in stage (i)with one or more acceleratedly in the presence of a catalytically effective amount of a catalytic composition including:

(a) one or more salts of alkaline earth metals and carboxylic acids or hydroxycarbonic acids and/or hydrates of the first;

(b) oxygen-containing acid selected from sulfuric acid and phosphoric acid;

(c) alcohol and/or ester;

and/or products of the interaction of (a),(b) and/or (c)

obtaining one or more acylated alkoxylated secondary alcohols.

DETAILED DESCRIPTION IS of the INVENTIONS

Stage (i) of the method according to the present invention includes the interaction of one or more internal olefins with one or more carboxylic acids in the presence of a catalytic composition with the formation of one or more esters of carboxylic acids.

These internal olefins, preferably selected from olefins, including 8-32 carbon atoms, more preferably from 10 to 28 carbon atoms and most preferably 12 to 24 carbon atoms.

Internal olefins used in stage (i) of the method according to the present invention may be substituted or unsubstituted aliphatic internal olefins.

Into groups substituted aliphatic internal olefins is not imposed specific restrictions, and they may include substituents selected from phenyl groups, 1-naftalina groups, 2-naftalina groups, peredelnyh groups, nitro groups, amino groups, aminogroup, halogen atoms, carboxyl groups, alkoxygroup (for example, methoxypropyl, taksigrup, fenoxaprop), kalkilya groups and heterocyclic groups.

Examples of internal olefins which are suitable for use in the method according to the present invention include a mixture of internal olefins formed in the partition isomerization-disproportionation of the way firms Shell for higher olefins (SHOP), neoba is consequently after passing through the isomerization of olefins (OIU) to increase the degree of branching is mainly linear internal olefins, emerging from the ID section to approximately one branching on the alkyl chain, for example, a mixture of C8-C10internal olefins, internal olefins, C10mixtures of C11-C12internal olefins, mixtures of C11-C14internal olefins, mixtures of C15-C16internal olefins and a mixture of C15-C18internal olefins. In addition, examples of internal olefins that can be used in the method according to the present invention include a mixture of internal olefins obtained in the method of converting paraffins by UOP (PACOL) in the stream of paraffins produced in the process of turning gas-liquid (GTL) or from the dewaxing process. In addition, in the method according to the present invention can be successfully applied a mixture of olefins formed directly in the way of synthesis of paraffins, olefins and oxaprozin Fisher-Tropsch.

On the carboxylic acid, which can be successfully applied in stage (i) of the method according to the present invention is not limited in any way. These carboxylic acids may be optionally substituted by one or more inert functional groups, i.e. functional groups that should not interfere with the reaction in stage (i). Examples of inert functional groups, which can be included in the composition of the acids include chlorine atoms and b is Ohm, nitro and alkoxygroup, for example metoxygroup.

Preferably, these carboxylic acids may be selected from branched and unbranched carboxylic acids comprising from 2 to 18 carbon atoms, more preferably from 2 to 12 carbon atoms and even more preferably from 2 to 8 carbon atoms.

Examples of aliphatic carboxylic acids which are suitable for use in the present invention include acetic acid, propionic acid, butyric acid and somaclonal acid.

Examples of aromatic carboxylic acids which are suitable for use in the present invention include benzoic acid, anisic acid, phenylacetic acid, o-Truelove acid, phthalic acid, isophthalic acid and terephthalic acid.

The interaction of olefins with carboxylic acids known in the art and described, for example, in“Organic Syntheses”, Collective Volume 4, ed. N.Rabjohn, John Wiley and Sons, New York, 1963, pp.261 and Chem.Commun. 2004, pp.1620. Typical methods of obtaining esters of carboxylic acids from olefins include the use of sulfuric acid as catalyst, and the use of various metal compounds, such as compounds comprising metals selected from copper, silver, gold, and ruthenium. In Chem.Commun., 2008, pp.777-779 describes several methods for producing esters of carboxylic acids from olefins. On reaccounted (i) not imposed any restrictions, and can successfully apply any of the known in the art methods.

However, in the preferred embodiment of the present invention stage (i) can be carried out in accordance with the methodology described in WO-A-2007/094211. I.e. in the preferred embodiment of the present invention, the catalytic composition used in stage (i)comprises (a) at least one compound of the metal, where the specified metal selected from iron, cobalt and Nickel; and (b) an acid compound.

The compound of the metal (a) in the specified catalytic composition is not limited, and a suitable connection can be, for example, from compounds having the General formula FeXn(where n represents 2 or 3), Fe(CO)5, Fe3(CO)12, Fe(CO)3(EN), Fe(CO)3DE, Fe(DE)2, CpFeX(CO)2, [CpFe(CO)2]2, [Cp*Fe(CO)2]2, Fe(acac)3, Fe(OAc)n(where n represents 2 or 3)CoX2, Co2(CO)8, Co(acac)n(where n represents 2 or 3), Co(OAc)2, CpCo(CO)2Cp*Co(CO)2, NiX2, Ni(CO)4, Ni(DE)2, Ni(acac)2and Ni(OAc)2.

In the above formulas, X represents a hydrogen atom, a halogen atom, preferably chlorine, a hydroxyl group, a cyano, alkoxygroup, carboxypropyl or thiocyanato group, Cp means cyclopentadienyls group, acac means the rest of acetylacetone, DE oznachaet is norbornadiene, 1, 5cyclooctadiene or 1.5-hexadiene, EN denotes ethylene or cyclooctene, and OAc means an acetate group.

Compounds of the metal (a), preferred for use in the catalytic compositions on stage (i) of the method according to the present invention, are compounds of iron. In the catalytic composition on the stage (i) of the method according to the present invention is particularly preferably the application of chloride of iron.

Acid compound (b), suitable for use in catalytic compositions on stage (i) of the method according to the present invention, preferably selected from acids of Bronsted or salts triftormetilfullerenov acid with metals.

Although there are no particular restrictions on the acid compound (ii), the preferred acid Bronsted include HCl, H2SO4, CF3SO3H, p-[CH3(CH2)11](C6H4)SO3H and acid sold under the trade name “NAFION” company E.I. du Pont de Nemours & Co., Inc.

Examples of salts triftormetilfullerenov acid with metals that are suitable for use in the method according to the present invention include Na(OSO2CF3), Li(OSO2CF3), Ag(OSO2CF3), Cu(OSO2CF3)2, Zn(OSO2CF3)2, La(OSO2CF3)3and Sc(OSO2CF3)3.

Acid Bronsted, suppose the equipment for use in catalytic compositions on stage (i) of the method according to the present invention, is triftormetilfullerenov acid, and the preferred salt triftormetilfullerenov acid with a metal suitable for use in catalytic compositions on stage (i) of the method according to the present invention is a silver salt triftormetilfullerenov acid.

The amount of acid compounds (b)used in the catalytic composition on the stage (i) of the method according to the present invention is not imposed specific restrictions, but the number of the specified acid compounds in relation to the number of connections of the metal (a), in molar terms, is preferably in the range of 1/300 to 10 and more preferably in the range of from 1/50 to 3.

The catalyst is designed for use on stage (i) of the method according to the present invention, preferable is a combination of the above-mentioned compounds of the metal (a) and the acid compound (b). However, in one embodiment, the implementation of each of the components, i.e. the compound of the metal (a) and the acid compound (b), can be obtained separately and added to the reaction mixture in stage (i). Alternatively, as described inChem.Commun., 2008, pp. 777-779, the compound of the metal (a) and the acid compound (b) can also be introduced into the reaction in advance, outside of the reaction mixture of stage (i), so that, for example, you can use salt meta is La and triftormetilfullerenov acid. Examples of such salts include Fe(OSO2CF3)3that can be obtained by the method described inCan.J.Chem., 1981, 59, 669-678.

The conditions of the reaction in stage (i) of the method according to the present invention is not limited in any way. However, in the preferred embodiment of the present invention stage (i) can be carried out at a temperature in the range from 20 to 300°C. and more preferably at a temperature in the range from 60 to 200°C.

The reaction of stage (i) of the method according to the present invention can be carried out in the presence of one or more inert solvents, i.e. solvents which do not inhibit the reaction of stage (i). Alternatively, the above reaction can be carried out in the absence of solvents.

Inert solvents which are suitable for use in stage (i) of the method according to the present invention, include, for example, hydrocarbons and ethers, more specifically, benzene, toluene, hexane, tetrahydrofuran, diethyl ether, disutility ether and dioxane.

Stage (ii) of the method according to the present invention includes the interaction of one or more esters of carboxylic acid, obtained in stage (i)with one or more acceleratedly in the presence of a catalytically effective amount of a catalytic composition comprising (a) one or more salts of alkali is onselling metals and carbon and/or hydroxycarbonic acids and/or hydrates of the first, (b) oxygen-containing acid selected from sulfuric acid and phosphoric acid, (c) alcohol and/or ester and/or products of the interaction of components (a), (b) and/or (c), with the formation of one or more acylated alkoxylates spirits.

The catalytic composition is intended for use on stage (ii) of the method according to the present invention can be obtained according to the method described in WO-A-02/38269. The specified catalytic composition preferably has the form of a visually homogeneous liquid suspension or a homogeneous paste.

The specified catalytic composition preferably includes one or more salts of alkaline earth metals and carbon and/or hydroxycarbonic acids and/or hydrates of the first and the oxygen-containing acid selected from sulfuric acid and phosphoric acid, in a total amount of from 10 to 65% by weight (wt.%) from the total mass of the specified catalytic composition.

If the catalytic composition used in stage (ii), includes only the components (a)-(c) and/or the products of interaction of components (a),(b) and/or (c), more preferably, these components are present in amounts in the ranges from 16 to 26 wt.% for (a), from 4 to 7 wt.% for (b) and from 67 to 80 wt.% for (c), in each case relative to the total weight of the catalytic composition.

Should the future in mind the exact quantity of components (a)-(c) selected from the above ranges so that the total amount was 100 wt.%.

The above catalytic composition can be obtained in the form of a concentrate in the form of visually homogeneous liquid or paste by mixing to achieve homogeneity of the so-called active ingredients a catalytic composition (a) and (b), and then adding the obtained homogeneous mixture of alcohols or esters (c), where these active ingredients are partially or completely insoluble in alcohols or ethers are used to obtain a concentrate of the catalyst, and esters of carboxylic acids, which are the source reagents exposed alkoxycarbonyl on stage (ii).

However, although the esters of carboxylic acids, obtained in stage (i) of the method according to the present invention can be effectively alkoxysilane on stage (ii) of the method according to the present invention using the above catalysts and reaction conditions according to WO-A-02/038269 and WO-A-2005/115964 formed the acylated alkoxylated alcohols, in particular ethoxylates methyl esters (MEE), may exhibit noticeable staining, in particular yellowing.

Accordingly, it was unexpectedly found that in the preferred embodiment of the present invention can be modificy the SQL catalytic composition, designed for use on stage (ii), in order to obtain the acylated alkoxylated alcohols having, in addition, the improved color properties, i.e. without any noticeable staining. These improved color properties are much more flexible in the production of detergents, which usually tend to get colorless, like water, liquid cleaning compositions or powder detergent compositions of white.

Therefore, particularly preferably, the catalytic composition is intended for use on stage (ii) of the method according to the present invention, included (a) one or more salts of the alkali earth metal and carbon and/or hydroxycarbonic acids and/or hydrates of the first, (b) oxygen-containing acid selected from sulfuric acid and phosphoric acid, (c) alcohol and/or ester, (d) peroxynitrate and/or its salt, and/or the products of interaction of components (a),(b),(c) and/or (d).

The specified catalytic composition unexpectedly gives a chance to get on stage (ii) is acylated alkoxylated alcohols, preferably of alkoxylated esters of fatty acids and more preferably of alkoxylated esters of fatty acids with a narrow range for the optional subsequent hydrolysis or transesterification (also known as transsilvania) at stage (iii)where the floor is obtained acylated alkoxylate spirits have improved color properties, in particular, a reduced yellowness.

In the specified preferred embodiment, if the specified catalytic composition comprises components (a)to(d) and/or food interaction (a), (b), (c) and/or (d), preferably, this composition included: (a) one or more salts of the alkali earth metal and carbon and/or hydroxycarbonic acids and/or hydrates of the first number in the range from 8 to 53 wt.%, more preferably in the range from 16 to 26 wt.%, by weight of the total catalyst composition; (b) oxygen-containing acid selected from sulfuric acid and phosphoric acid, in an amount in the range from 2 to 13%, more preferably in the range of 4 to 7 wt.% by weight of the total catalyst composition; (c) alcohol and/or ester in an amount in the range from 34 to 90 wt.%, more preferably in the range from 67 to 80 wt.% by weight of the total catalyst composition; and (d) peroxynitrate and/or its salt in an amount in the range from 10 to 10,000 parts per million (weight/weight), more preferably in the range from 30 to 3000 parts per million (weight/weight), and most preferably in the range from 100 to 1000 parts per million (weight/weight) of the total weight of the catalytic composition, and/or the products of interaction of components (a), (b), (c) and/or (d).

It should be the go the exact quantity of components (a)-(d) selected from the above ranges so that their total number was 100 wt.%.

Salts of alkaline earth metals (a), which are suitable for use in catalyst compositions for the stage (ii) of the method according to the present invention include the salts of calcium or magnesium, and carbon and/or hydroxycarbonic acids and/or hydrates of the former.

If salts of alkaline earth metal (a) are salts of carboxylic acids, particularly preferably, these salts were derived from the same or of the same carboxylic acid, which was used in stage (i) of the method according to the present invention.

Salts that are suitable for use as component (a) catalytic compositions for the stage (ii) of the method according to the present invention are salts of carboxylic and/or hydroxycarbonic acids of low molecular weight, i.e. carboxylic and/or hydroxycarbonic acids comprising 1-18 carbon atoms.

Preferred salts are salts of carboxylic acids comprising 1 to 7 carbon atoms, and/or salts hydroxycarbonic acids comprising 2 to 7 carbon atoms.

The preferred salts are salts of carboxylic acids, comprising 2-4 carbon atoms and/or salts hydroxycarbonic acids comprising 2-4 carbon atoms.

Examples of salts that could is t be used as component (a) in the catalytic compositions for the stage (ii) of the method according to the present invention, include salts of formic acid, acetic acid, propionic acid, lactic acid, somaclonal acid, 2-hydroxy-2-methylpropanoic acid and benzoic acid.

Preferred are calcium salts of carboxylic and/or hydroxycarbonic acids comprising 1-18 carbon atoms, preferably 1-7 carbon atoms, more preferably 2-4 carbon atoms and/or hydrates of the former.

Examples of such calcium salts include calcium acetate, and/or calcium lactate, and/or hydrate first.

Specific examples of oxygen-containing acids suitable for use in catalytic compositions are concentrated (85%) phosphoric acid and concentrated (95-97%) sulfuric acid.

Alcohol, which can be used as component (c) in the catalytic compositions for the stage (ii) of the method according to the present invention may be primary, secondary or tertiary alcohol.

Alcohol and/or ester used as component (c) in the catalytic compositions for the stage (ii) of the method according to the present invention, preferably an alcohol comprising from 1 to 6 carbon atoms and/or ether carboxylic acids comprising from 2 to 39 carbon atoms. In a particularly preferred embodiment of the present invention, the ester component (c) can be and is koksilinon.

Examples of alcohols and esters that are suitable for use as component (c) in the catalytic compositions for the stage (ii) of the method according to the present invention include methanol, ethanol, propanol, 2-propanol (isopropyl alcohol), butanol, 2-butanol (sec-butyl alcohol) and 2-methyl-2-propanol (tert-butyl alcohol), pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol (isoamyl alcohol), 2,2-dimethyl-1-propanol (neopentylene alcohol), 2-methyl-2-butanol (tert-amyl alcohol), hexanol, 2-hexanol, 3-hexanol, methylformate, ethyl formate, paperformat, isopropylpalmitate, bodyformat, second-bodyformat, isobutylparaben, interformat, italicformat, mexifornia, cyclohexylurea, gadiformes, benzoylformate, ochiltree, noninformed, 1-dezinformeet, esters of formic acid and second-Danilovich alcohols, such as 2-decanol, 3-decanol, 4-decanol and 5-decanol and mixtures thereof, esters of formic acid and a mixture of second-undecylenic alcohols and second-dodecyloxy alcohols, 1-dadesiforum, esters of formic acid and second-dodecyloxy alcohols, such as 2-dodecanol, 3-dodecanol, 4-dodecanol, 5-dodecanol and 6-dodecanol and mixtures thereof, esters of formic acid and a mixture of second-tridecanoic alcohols and second-tetradecenoic alcohols, esters of formic acid and a mixture of linear or branched second-pentadecenoic alcohols and second-GE is sadulovich alcohols or a mixture of linear or branched second-pentadecenoic alcohols, second-hexadecenoic alcohols, sec-heptadecenoic alcohols and second-octadecenoic alcohols, esters of formic acid and a mixture of second-nonadecanoic alcohols, sec-ansilove alcohols, sec-heneicosanol alcohols, sec-docosenoic alcohols, sec-triazolovy alcohols, sec-tetracosanoic alcohols, sec-pentacosanoic alcohols, sec-hexacosanol alcohols, sec-heptacosanoic alcohols, sec-octacosanol alcohols, sec-nonacosanoic alcohols, sec-triacontanoic alcohols, sec-hentriacontane alcohols or second-dotriacontanoic alcohols, methyl acetate, ethyl acetate, propyl, isopropylacetate, butyl acetate, sec-butyl acetate, isobutyl acetate, tert-butyl acetate, pentalateral, 2-pentalateral, 3-pentalateral, isoamylase, tert-amylacetate, exilerated, cyclohexylacetate, heptylate, benzoylacetate, octylated, nonracemic, decelerated, the acetic acid esters and secondary alcohols, such as 2-decanol, 3-decanol, 4-decanol and 5-decanol and mixtures thereof, esters of acetic acid and a mixture of second-undecylenic alcohols and second-dodecyloxy alcohols, 1-dodecalactam, the acetic acid esters and second-dodecyloxy alcohols, such as 2-dodecanol, 3-dodecanol, 4-dodecanol, 5-dodecanol and 6-dodecanol and mixtures thereof, esters of acetic acid and a mixture of second-tridecanoic alcohols and second-tetradecenoic alcohols, esters of acetic acid and a mixture of the linear and the branched second-pentadecenoic alcohols and second-hexadecenoic alcohols or a mixture of linear or branched second-pentadecenoic alcohols, second-hexadecenoic alcohols, sec-heptadecenoic alcohols and second-octadecenoic alcohols, esters of acetic acid and a mixture of second-nonadecanoic alcohols, sec-ansilove alcohols, sec-heneicosanol alcohols, sec-docosenoic alcohols, sec-triazolovy alcohols, sec-tetracosanoic alcohols, sec-pentacosanoic alcohols, sec-hexacosanol alcohols, sec-heptacosanoic alcohols, sec-octacosanol alcohols, sec-nonacosanoic alcohols, sec-triacontanoic alcohols, sec-hentriacontane alcohols or second-dotriacontanoic alcohols, methylisobutyl, utilizabilitate, propresenter, isopropyltoluene, utilitatera, second-utilitatera, isobutylester, tert-utilitatera, pantiesamatur, 2-pantiesamatur, 3-pantiesamatur, isomerization, tert-amelioration, hexylester, cyclohexanebutyrate, peptidesort, benzylester, attributeset, nonresolution, declinometer, esters somaclonal acid and second-Danilovich alcohols, for example, 2-decanol, 3-decanol, 4-decanol and 5-decanol and mixtures thereof, esters somaclonal acid and a mixture of second-undecylenic alcohols and second-dodecyloxy alcohols, 1-dodecylsulfonate, esters somaclonal acid and second-dodecyloxy alcohols, for example 2-dodecanol, 3-dodecanol, 4-dodecanol, 5-dodecanol and 6-dodecanol and mixtures thereof, esters somaclonal kislotye mixture of second-tridecanoic alcohols and second-tetradecenoic alcohols, esters somaclonal acid and a mixture of linear or branched second-pentadecenoic alcohols and second-hexadecenoic alcohols or a mixture of linear or branched second-pentadecenoic alcohols, sec-hexadecenoic alcohols, sec-heptadecenoic alcohols and second-octadecenoic alcohols, ethers somaclonal acid and a mixture of second-nonadecanoic alcohols, sec-ansilove alcohols, sec-heneicosanol alcohols, sec-docosenoic alcohols, sec-triazolovy alcohols, sec-tetracosanoic alcohols, sec-pentacosanoic alcohols, sec-hexacosanol alcohols, sec-heptacosanoic alcohols, sec-octacosanol alcohols, sec-nonacosanoic alcohols, sec-triacontanoic alcohols, sec-hentriacontane alcohols or second-dotriacontanoic alcohols, methylbenzoate, ethylbenzoic, propylbenzoate, isopropylbenzoic, butylbenzoate, second-butylbenzoate, isobutylene, tert-butylbenzoate, pentylbenzoic, 2-pentylbenzoic, 3-pentylbenzoic, isoamylase, tert-Levental, hexylbenzoate, cyclohexylbenzene, heptylbenzoic, benzyl benzoate, octylbenzoic, nonvented, delventhal, esters of benzoic acid and second-Danilovich alcohols, such as 2-decanol, 3-decanol, 4-decanol and 5-decanol, and mixtures thereof, esters of benzoic acid and a mixture of second-undecylenic alcohols and second-dodecyloxy alcohols, 1-dodecyl benzoate, esters of benzoic acid and second-dodecyloxy sleep is tov, for example, 2-dodecanol, 3-dodecanol, 4-dodecanol, 5-dodecanol and 6-dodecanol and mixtures thereof, esters of benzoic acid and a mixture of second-tridecanoic alcohols and second-tetradecenoic alcohols, esters of benzoic acid and a mixture of linear or branched second-pentadecenoic alcohols and second-hexadecenoic alcohols or a mixture of linear or branched second-pentadecenoic alcohols, sec-hexadecenoic alcohols, sec-heptadecenoic alcohols and second-octadecenoic alcohols, esters of benzoic acid and a mixture of second-nonadecanoic alcohols, sec-ansilove alcohols, sec-alcohols heneicosane, second-docosenoic alcohols, sec-triazolovy alcohols, sec-tetracosanoic alcohols, sec-pentacosanoic alcohols, sec-hexacosanol alcohols, sec-heptacosanoic alcohols, sec-octacosanol alcohols, sec-nonacosanoic alcohols, sec-triacontanoic alcohols, sec-hentriacontane alcohols or second-dotriacontanoic alcohols, metaloprokat, ethylcaproic, isopropylcarbonate, methylophilus, eticaret, isopropylcarbamate, methylcitrate, eticaret, isopropylmalate, meilleur, tillaart, isopropylene, metalmeister, atelierista, isopropylmyristate, metrpolitan, Etisalat, isopropyl, methyltert, telstart, isopropylene, methyl oleate, etiloleat, isopropylacetate, meilleret, ethyllinoleate, isopropylindole, m is illinoisat, amillenialist, isopropylaniline, mediarakyat, amiloride, isopropylacetate, metalagen, activegantt, Isopropylamine and mixtures thereof.

In one of the embodiments of the present invention, the catalytic composition used in stage (ii)includes as a component (c) ester, which coincides with exposed alkoxycarbonyl complex ether carboxylic acid, obtained in stage (i).

Peroxynitrate, which optionally can be used as component (d) in the catalytic compositions for the stage (ii) of the method according to the present invention, can be successfully selected from percarbonic acids, perhalogenated acids, hypoallegenic acids, nedovolnoj acid, perarnau acid, Pervozvanny acid, nadkarni acid and mixtures thereof.

Salt peroxyketal that are suitable for use include ammonium salts, alkali metal and/or alkaline earth metals. Examples of preferred salts of alkali metals and alkaline earth metals include sodium, potassium, magnesium and barium.

Examples of particularly preferred salts peroxyketal are persulfates of ammonium, alkali metals and alkaline earth metals, in particular persulfates of ammonium, sodium, potassium and barium. Preferred is ammonium persulfate (also known as peroxidised is tons of ammonium, (NH4)2S2O8). These salts are commercially available.

As mentioned above, in the preferred embodiment of the present invention, the catalytic composition used in stage (ii) of the method according to the present invention, has the form of a visually homogeneous liquid suspension or a homogeneous paste.

In one of the embodiments, the catalytic composition used in stage (ii) of the method according to the present invention can be applied in the form of fresh, finely ground (for example, in a colloid mill, a ball mill or by means of an ultrasonic homogenizer, for example, “Labsonic P” with a maximum power of 400 W, manufactured by Sartorius AG, Goettingen, Germany) mixture of components (a)-(c) and optionally (d).

For example, if the specified catalytic composition comprises components (a)to(d) and/or food interaction (a), (b), (c) and/or (d), the catalytic composition of the present invention can be successfully prepared, first, by mixing peroxyacids and/or its salts with oxygen-containing acid with getting peroxidebased acid solution, including peroxynitrate or peroxisome in number, in the range from 0.02 to 20 wt.%, more preferably in the range from 0.06 to 6 wt.% and most preferably in di the range from 0.2 to 2 wt.% from the total mass of peroxyacids and/or its salts and oxygen-containing acid.

This peroxidase acid solution slowly with vigorous stirring and mixed with a suspension of one or more salts of alkaline earth metals and carbon and/or hydroxycarbonic acids and/or hydrates of the first, in alcohol and/or ether complex at a temperature generally in the range from 283 to 368 K, preferably at a temperature of less than 313 K.

For example, in the preferred embodiment, 0.55 wt.% solution peroxydisulfate in concentrated ammonium (95-97%) sulfuric acid can be mixed with the suspension monohydrate calcium acetate or calcium lactate with vigorous stirring with such speed that the temperature did not rise above 313 K, even more preferably at such a speed that the temperature was below 303 K.

In a particularly preferred embodiment, 0.55 wt.% solution peroxydisulfate in concentrated ammonium (95-97%) sulfuric acid can be mixed with the suspension monohydrate calcium acetate with vigorous stirring with such speed that the temperature did not rise above 303 K, then process the suspension ultrasonic mixing device at a temperature below 303 K in 1 minute.

In a particularly preferred embodiment of the present invention, the specified catalytic composition comprises (a) od is at or more salts of alkali metals and carbon and/or hydroxycarbonic acids and/or hydrates of the first, (b) oxygen-containing acid selected from sulfuric acid and phosphoric acid, (c) alcohol and/or ester and (d) peroxynitrate and/or its salt, and/or the products of interaction of components (a), (b), (c) and/or (d)where the specified composition obtained by homogenization, and components (a) and (b) are present in amounts in the range from 10 to 65 wt.% in relation to the total weight of the catalytic composition, which is calculated from the fractions of components (a)to(d), to be applied upon receipt of the catalyst.

The catalytic composition is intended for use on stage (ii) of the method according to the present invention can be used in a catalytically effective amount, i.e. in an amount sufficient to accelerate the reaction alkoxysilane or influence on the distribution of the number alkalinising fragments in the molecules of the product. Although the specific amount of catalyst is not critical for the method of the present invention, it is preferable to apply the specified catalytic composition at stage (ii) in an amount of not less than 0.05 wt.%, although typical embodiments more preferably a number in the range from 0.2 to 5 wt.% and most preferably a number in the range from 0.5 to 2 wt.%. These percentages correspond to the weight of the catalytic composition, introduced in the reaction is second mixture, in relation to the total weight of the product of stage (i) after removal of volatile components (e.g., solvent and/or excess carboxylic acid) from a specified stage of the reaction mixture (i).

At stage (ii) can be applied to significantly larger quantities specified catalytic composition, for example, up to 10 wt.% or more. As a rule, the higher the desired number alkalinising fragments in alkoxylate the product and the higher the desired reaction rate, the greater the required amount of catalyst.

In response alkoxysilane on stage (ii) of the method according to the present invention suitable acceleratedly (epoxy) reagents can be selected from one or more vicinal alkalisation, in particular lower alkalisation, and more specifically comprising 2-4 carbon atoms. In General, these alkalinity can be represented by the formula

where each of the fragments of R1,R2,R3and R4individually selected from the group consisting of hydrogen and alkyl groups. More preferred are compounds which include ethylene oxide, propylene oxide or mixtures of ethylene oxide and propylene oxide, especially those that are mainly composed of ethylene oxide and propylene oxide. Acceleratedly reagents, consisting mainly of ethylene oxide, are considered the most is preferable from the standpoint of commercial opportunities for the practical implementation of the process alkoxysilane, and from the point of view of obtaining products with a narrow range of distribution ethylenoxide deputies.

Preferred esters of carboxylic acids, obtained in stage (i) and intended for subsequent introduction into the reaction in stage (ii) of the method according to the present invention include esters of formic acid, acetic acid, propionic acid, butyric acid, somaclonal acid, pentanol acid, Caproic acid, and optionally substituted benzoic acids, such acids, in which one or more hydrogen atoms of the benzene ring is substituted by one or more inert functional groups, i.e. functional groups that do not participate in the reaction in stage (ii). Examples of inert functional groups which may be present as substituents include chlorine atoms and bromine, nitro and alkoxygroup, for example metoxygroup.

The preferred esters of carboxylic acids, obtained in stage (i) and intended for further introduction into the reaction in stage (ii) of the method according to the present invention are esters of acetic acid, ethers somaclonal acid, esters of benzoic acid and esters of fatty acids.

Examples of these fatty acid esters include esters of Caproic acid, Caprylic acid, Caprino is Oh acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachnid acid, beganovi acid and mixtures thereof.

Esters of carboxylic acids and, in particular, esters of fatty acids, which are suitable for use in the process of alkoxysilane on stage (ii) of the method according to the present invention, after receiving them on stage (i)include, for example, sec-butyl esters, sec-amyl ether and tert-amyl esters, sec-delloye ethers, such as 2-delloye, 3-delloye, 4-delloye and 5-delloye esters and mixtures thereof, second-undecylate esters, sec-dodecylamine ethers, such as 2-undecylate, 3-undecisive, 4-undecylate, 5-undecylate, 2-dodecylamine, 3-dodecyloxy, 4-dodecyloxy, 5-dodecylamine and 6-dodecylamine esters and mixtures thereof, second-tridecylamine esters and second-tetradecane ethers, such as 2-tridecylamine, 3-tridecylamine, 4-tridecylamine, 5-tridecylamine, 6-tridecylamine, 2-tetradecyl, 3-tetradecyl, 4-tetradecyl, 5-tetradecane, 6-tetradecane, 7-tetradecyl esters and mixtures thereof, second-pentadecanolide esters, sec-hexadecylamine esters, sec-heptadecyl esters, sec-octadecylamine esters and mixtures thereof, second-nonadecanone esters, sec-ansilove esters, sec-heneicosane esters, sec-dorazilova esters, sec-triazolone esters, sec-tetracosyl the e esters, second-pentacosane esters, sec-hexacosane esters, sec-heptacosane esters, sec-octacosane esters, sec-nonacosane esters, sec-triacontane esters, sec-hentriacontane esters, sec-dotriacontane esters and mixtures thereof.

Preferred esters of carboxylic acids that are suitable for use in the process of alkoxysilane on stage (ii) of the method according to the present invention, after receiving them on stage (i), include second-butyl, sec-amyl, tert-amyl, sec-decyl, such as 2-decyl, 3-decyl, 4-decyl -, and 5-decyl, sec-undecyl, sec-dodecyl, such as 2-undecyl, 3-undecyl, 4-undecyl, 5-undecyl, 2-dodecyl, 3-dodecyl, 4-dodecyl, 5-dodecyl and 6-dodecyl, sec-tridecyl, sec-tetradecyl, for example 2-tridecyl, 3-tridecyl, 4-tridecyl, 5-tridecyl, 6-tridecyl, 2-tetradecyl, 3-tetradecyl, 4-tetradecyl, 5-tetradecyl, 6-tetradecyl, 7-tetradecyl, second-pentadecyl, second-hexadecyl, second-heptadecyl, sec-octadecyl, second-Needell, second-eicosyl, second-heneicosan, second-docosyl, second-tricosal, Deut-tetracosyl, second-pentasil, second-hexagonal, second-heptagonal, second-octacosyl, second-nonkosi, second-triacontyl, second-hentriacontane and second-dotriacontane acetates and mixtures thereof.

Another preferred class of esters of carboxylic acids that may be suitable for use in the reaction of alkoxysilane on stage (ii) of the method according to the present invention, p is following their receipt at the stage (i), includes second-butyl, sec-amyl, tert-amyl, sec-decyl, such as 2-decyl, 3-decyl, 4-decyl -, and 5-decyl, sec-undecyl, sec-dodecyl, such as 2-undecyl, 3-undecyl, 4-undecyl, 5-undecyl, 2-dodecyl, 3-dodecyl, 4-dodecyl, 5-dodecyl and 6-dodecyl, sec-tridecyl, sec-tetradecyl, for example 2-tridecyl, 3-tridecyl, 4-tridecyl, 5-tridecyl, 6-tridecyl, 2-tetradecyl, 3-tetradecyl, 4-tetradecyl, 5-tetradecyl, 6-tetradecyl, 7-tetradecyl, second-pentadecyl, second-hexadecyl, second-heptadecyl, sec-octadecyl, second-Needell, second-eicosyl, second-heneicosan, second-docosyl, second-tricosal, second-tetracosyl, second-pentasil, second-hexagonal, second-heptagonal, second-octacosyl, second-nonkosi, second-triacontyl, second-and hentriacontane second-dotriacontane isobutyrate and mixtures thereof.

Another preferred class of esters of carboxylic acids that may be suitable for use in the process of alkoxysilane on stage (ii) of the method according to the present invention, after receiving them on stage (i), includes second-butyl, sec-amyl, tert-amyl, sec-decyl, such as 2-decyl, 3-decyl, 4-decyl -, and 5-decyl, sec-undecyl, sec-dodecyl, such as 2-undecyl, 3-undecyl, 4-undecyl, 5-undecyl, 2-dodecyl, 3-dodecyl, 4-dodecyl, 5-dodecyl and 6-dodecyl, sec-tridecyl, sec-tetradecyl, for example 2-tridecyl, 3-tridecyl, 4-tridecyl, 5-tridecyl, 6-tridecyl, 2-tetradecyl, 3-tetradecyl, 4-tetradecyl, 5-tetradecyl, 6-tetradecyl, 7-t is tridecyl, second-pentadecyl, second-hexadecyl, second-heptadecyl, sec-octadecyl, second-Needell, second-eicosyl, second-heneicosan, second-docosyl, second-tricosal, second-tetracosyl, second-pentasil, second-hexagonal, second-heptagonal, second-octacosyl, second-nonkosi, second-triacontyl, second-hentriacontane and second-dotriacontane benzoate and mixtures thereof.

As for the method of conducting the reaction, alkoxysilane on stage (ii) of the method according to the present invention can be performed basically in the usual way. For example, the catalytic composition used in stage (ii), together with liquid ether carboxylic acid, obtained in stage (i), you can enter into contact preferably with stirring with alkalization, which is usually injected in gaseous form, at least in the case of the lower alkalisation.

An additional quantity of liquid ether carboxylic acid, obtained in stage (i), optionally you can add at any time prior to the introduction of accelerated. Thus, it is possible to obtain a concentrated reaction mixture with a catalyst and can be used by parts if necessary.

In preferred embodiments of the method of the present invention, alkalinity reagent is an ethylene oxide or propylene oxide, or a mixture of ethylene oxide and propylene oxide.

In especially preferred is the embodiment, at stage (ii) ethylene oxide is introduced into the contact and interaction with the ether carboxylic acid, obtained in stage (i), preferably a fatty acid ester, in the presence of a catalytically effective amount of a catalytic composition for alkoxysilane described in this application. When conducting stage (ii) at any time you don't need to add an additional portion of the liquid ether carboxylic acid, obtained in stage (i).

In another embodiment of the present invention the reaction alkoxysilane on stage (ii) can be carried out according to the method described in WO-A-2005/115964, which is incorporated into the present application by reference.

I.e. in one of the embodiments, the reaction alkoxysilane on stage (ii) of the method according to the present invention includes an introduction alkalinizing reagent into the reactor, in which the ether carboxylic acid, obtained in stage (i), in the presence of catalytic compositions described in the text of this application, and the reactor filled part (x') provided the total number (X) ether carboxylic acid, obtained in stage (i), which is assumed to be alkoxycarbonyl, and all pre-planned by the number (Y) of the catalytic composition, after which the reactor is injected another portion (z') total pre-planned the number (Z) alkalinizing reagent, to activate mentioned catalytic composition and the initiation of the reaction, and after the entered number (z') alkalinizing reagent undergoes complete or partial transformation, add a portion of the ether carboxylic acids with additional ether carboxylic acid, obtained in stage (i), to a pre-planned number (X) and continue to serve alkalinity reagent prior to the introduction of a pre-agreed period number (Z), preferably to the portion (x') ether carboxylic acid, obtained in stage (i), introduced at the initial stage of the synthesis, was as small as possible in relation to a common pre-determined quantity of ether carboxylic acids (X)obtained in stage (i), i.e., this quantity is approximately equal to the minimum number set for this reactor, which means that the magnitude of the quotient from dividing x'/X is the minimum possible.

Although the above-described method refers to the periodic process of synthesis, the method according to the present invention are equally applicable to a continuous process.

In General, two reagent at stage (ii) is applied in predetermined amounts to obtain the product alkoxysilane with the desired average number of attached fragments. This is the average number of attached fragments is found in the product does not play a decisive role in the method according to the present invention. The products obtained according to the method of the present invention typically have an average number of connected fragments range from less than 1 to 30 or more.

In General, temperature and pressure, which are suitable for the reaction of alkoxysilane on stage (ii) of the method according to the present invention are the same as in the usual reactions alkoxysilane between the same reagents using conventional catalysts. As a rule, from the viewpoint of the reaction rate preferred temperature of at least 90°C, in particular at least 120°C and more specifically not less than 130°C, whereas temperatures less than 250°C, in particular less than 210°C and, more specifically, less than 190°C, usually desirable to minimize the destruction of the product. As is known in the art, the reaction temperature can be optimized for a specific reagents, taking into account the above factors.

For stage (ii) is preferably a pressure higher than atmospheric, for example excessive pressure in the range of 0.7 to 1 MPa (from about 10 to about 150 psi, and this pressure is usually sufficient to maintain ether carboxylic acid, obtained in stage (i), mainly in the liquid state at the reaction in stage (ii).

If the ether carboxylic acid, obtained in stage (i)is liquid and accelerated, as a result, the output at stage (ii), is in a gaseous state, alkoxysilane on stage (ii) is conveniently made by injection accelerated in under pressure reactor containing liquid ether carboxylic acid and a catalytic composition. For security reasons, reactions, alkalinity reagent is preferably diluted with an inert gas, such as nitrogen, for example, to the concentration in the gas phase to about 50 volume percent or less. However, the reaction in stage (ii) may be safely performed at higher concentrations of accelerated, higher total pressure and a higher partial pressure of accelerated, if you take proper precautions, known in the art, to prevent the danger of explosion.

The time required to complete the reaction alkoxysilane on stage (ii), depends on the desired degree of alkoxysilane (i.e. the average number alkalinising fragments in the product), and reaction rate alkoxysilane (which, in turn, depends on the temperature, amount of catalyst, amount of catalyst and the nature of the reagents). Typically the reaction in preferred variants of implementation, in particular, for the case when alkalinized is gaseous, is less than 12 hours. If alkalinized is applied ethylenoxy is, typically the reaction is less than 5 hours. If accelerated propylene oxide is used, the sample time of the reaction is less than 8 hours.

After completion of the reaction alkoxysilane on stage (ii) the product is preferably cooled. If so desired, can be removed from the product of the catalytic composition. In those embodiments, the implementation of the present invention, where one or more acylated alkoxylated secondary alcohols obtained in stage (ii), to be introduced in the subsequent optional stage (iii) to hydrolysis or transesterification mentioned one or more acylated alkoxylated secondary alcohols with the purpose of obtaining one or more alkoxylated secondary alcohols, the catalyst removal to the implementation stage (iii) is not necessary.

The remains of the catalyst can be separated from one or more acylated alkoxylated secondary alcohols obtained in stage (ii), for example, by filtration, deposition, or extraction. It was found that a number of specific ways physical or chemical treatment facilitates the removal of residual catalyst from the liquid product of stage (ii). These methods include the contact product alkoxysilane with strong acids, such as phosphoric and/or oxalic acid or solid fuel is hard organic acids, for example, sold under the trade name “NAFION” H+ (E.I. du Pont de Nemours & Co., Inc.) and “AMBERLITE” IR 120H (Rohm & Haas Co.) from Sigma-Aldrich; contact with carbonates and bicarbonates of alkali metals; contact with the zeolites, such as zeolite type Y or mordenite; or contact with some clays. Typically, the processing is followed by filtration or sedimentation of solids from the product. In many cases, filtration, sedimentation or centrifugation is most effective at higher temperatures.

The preferred compositions of acidified alkoxylated secondary alcohols, which can be obtained by carrying out steps (i) and (ii) of the method according to the present invention, for optional subsequent hydrolysis or transesterification (also known as "transsilvania") at the stage (iii), are those compositions that include one or more acylated alkoxylated secondary alcohols, in particular alkoxycarbonyl esters of fatty acids having formula (I):

R1-C(O)-(OA)n-OR2(I)

where R1is a linear or branched alkyl group comprising from 1 to 30 carbon atoms, optionally substituted cycloalkyl group comprising from 5 to 30 carbon atoms, or optionally substituted aryl group comprising from 6 to 30 carbon atoms, OA Osnach the et one or more oxyalkylene fragments, which may be the same or different, and n means an integer in the range from 0 to 70, and R2is a linear or branched alkyl group comprising from 4 to 32 carbon atoms, optionally substituted cycloalkyl group comprising from 5 to 32 carbon atoms, or optionally substituted bicycloalkyl group including from 7 to 32 carbon atoms.

Especially preferred acylated by alkoxylated secondary alcohols, including alkoxylate esters of fatty acids, which can be obtained by carrying out steps (i) and (ii) of the method according to the present invention, for optional subsequent hydrolysis stage (iii)are such alkoxylate, in which R1means a linear or branched alkyl group containing 1-22 carbon atoms or optionally substituted phenyl group, the segment OA is independently selected from oksietilenovomu and oxypropylene fragment, n means an integer in the range from 1 to 30, and R2is a linear or branched alkyl group comprising from 4 to 32 carbon atoms.

The acylated alkoxylated secondary alcohols, which can be obtained by carrying out steps (i) and (ii) of the method according to the present invention, for subsequent optional hydrolysis stage (iii), and which are especially preferred is Holocene detergents, are such compounds of formula (I)in which R1means optionally substituted phenyl group, preferably phenyl group, hydrogen or an alkyl group containing 1-22 carbon atoms, preferably 1 carbon atom, a fragment of OA independently selected from oksietilenovomu or oxypropylene fragment, n means an integer in the range from 1 to 30, and R2is a linear or branched alkyl group comprising from 4 to 32 carbon atoms.

In one of the embodiments of the present invention, the preferred acylated alkoxylated secondary alcohols is a composition of alkoxylated acetic acid esters, i.e. compounds of formula (I)in which R1means methyl group, the segment OA is independently selected from oksietilenovomu and oxypropylene fragment, n means an integer in the range from 1 to 30, and R2is a linear or branched alkyl group comprising from 4 to 32 carbon atoms.

Alkoxylate esters of fatty acids, which can be obtained by carrying out steps (i) and (ii) of the method according to the present invention, for subsequent optional hydrolysis stage (iii), and which are especially preferred for obtaining detergents, are such compounds of formula (I)in which R1oznacza the t alkyl group, comprising from 6 to 22 carbon atoms, preferably from 9 to 15 carbon atoms, a fragment of OA independently selected from oksietilenovomu and oxypropylene fragment, n means an integer in the range from 1 to 30, and R2is a linear or branched alkyl group comprising from 4 to 32 carbon atoms, preferably from 4 to 6 carbon atoms.

In the formula (I) various fragments of OA can be randomly distributed along alkoxide chain or they may be provided in the circuit in the form of a block(co)polymers.

You can make an optional stage (iii), including the hydrolysis or transesterification (also known as transsilvania) to release one or more alkoxylated secondary alcohols with one or more acylated alkoxylated secondary alcohols obtained in stage (ii).

Stage (iii) can be conducted under conditions well known in the art for the reactions of hydrolysis and transesterification. The temperature at which you can successfully carry out this stage, is in the range from 0 to 200°C, preferably in the range from 50 to 150°C. the Pressure at which it is possible to successfully carry out the reaction generally is atmospheric pressure, although you can also apply high or low blood pressure. As a rule, to increase the speed of the interesterification reaction note the observed acidic or basic catalysts in amounts < 10% (mol/mol) (in relation to the number of acylated alkoxylate secondary alcohol). Examples of acid catalysts are p-toluensulfonate acid, sulfuric acid and phosphoric acid, and examples of the basic catalyst is tert-piperonyl potassium. Alcohols which are suitable for the transesterification of one or more acylated alkoxylated secondary alcohols obtained in stage (ii)include methanol, ethanol, isopropyl alcohol and tert-butyl alcohol.

Alkoxylated secondary alcohols obtained in stage (iii) of the method according to the present invention, it is possible to sulfotyrosine with getting alkoxylated secondary alcohols.

Accordingly, in another embodiment of the present invention, further developed the method of obtaining alkoxylated secondary alcohols, including sulfation of alkoxylated secondary alcohols, obtained as described above.

I.e. in the present invention, among other things, developed a method of obtaining alkoxylated secondary alcohols, which includes stages:

- get alkoxylated secondary alcohols as described above; and

- sulfation of alkoxylated secondary alcohols.

Sulfotyrosine agents suitable for use include agents containing sulfur trioxide complexes of sulfur trioxide with grounds (Lewis) such as a complex of sulfur trioxide with pyridine and a complex of sulfur trioxide with trimethylamine, chlorosulfonic acid and sulfamoyl acid.

The sulfation reaction can be conducted at a temperature of preferably not more than 80°C. the Sulfation can be performed at a low temperature of approximately -20°C, but higher temperatures are better from the economic point of view. For example, sulfation can be successfully carried out at a temperature in the range from 20 to 70°C, preferably in the range of from 20 to 60°C and more preferably in the range of from 20 to 50°C. sulfur Trioxide is the most cost-effective sulfatrim agent.

Alkoxylated secondary alcohols can enter into interaction with a gas mixture which, in addition, at least one inert gas contains from 1 to 8 percent by volume (vol.%) from the volume of a gas mixture of gaseous sulfur trioxide, preferably from 1.5 to 5 vol.%. In principle it is possible to apply a gas mixture comprising less than 1 % by volume of sulfur trioxide, but unacceptably reduced space-time yield. The use of mixtures with an inert gas containing more than 8 vol.% sulfur trioxide, as a rule, can lead to problems associated with uneven sulfation, temperature instability and increased formation of undesirable side products. Although for the reaction of the other inert the basics, preferred are air or nitrogen, as a rule, because of their high availability.

The interaction of alkoxylate secondary alcohol with sulfur trioxide contained in the inert gas, can be carried out in reactors with descending liquid film. In reactors of this type uses a liquid film flowing down a thin layer on the cooled wall, which is brought into contact with the permanent gas stream. As possible reactors could come cascades of reactor vessels. Other types of reactors include vessel with stirring, which can be applied if the sulfation is carried out with the use of sulfonovoj acid or a complex of sulfur trioxide and grounds (Lewis), such as a complex of sulfur trioxide with pyridine or a complex of sulfur trioxide with trimethylamine. These sulfotyrosine agents could give the possibility of increasing the time of sulfation without the risk of destruction ethoxylate chain and elimination of olefin under acid catalysis (Lewis).

The molar ratio of sulfur trioxide and alkoxylate may be in the range of 1.4 to 1 or less, including in the range from 0.8 to 1 mole of sulfur trioxide per mole of OH groups alkoxylate, and the last value is preferred. For sulfation of alkoxylated you can apply sulfur trioxide, and the temperature can be in di the range from -20 to 50°C, preferably from 5 to 40°C and an absolute pressure may be in the range from 100 to 150 kPa. The reaction can be carried out in continuous or batch mode. The time of reaction of sulfation may be in the range of 0.5 seconds to 10 hours, but is preferably from 0.5 seconds to 20 minutes.

The sulfation can be performed with the use of chlorosulfonic acid at a temperature in the range from -20 to 50°C, preferably from 0 to 30°C. the Molar ratio between alkoxylates and chlorosulfonic acid may be in the range from 1:0.8 to 1:1,2, preferably from 1:0.8 to 1:1. The reaction can be carried out in continuous or batch mode during the period of time from a fraction of a second (i.e. 0.5 seconds) to 20 minutes.

You should exclude the application of the sulfation reaction of sulfuric acid and oleum, if these reagents are used only to generate gaseous sulfur trioxide. The effect of these reagents on any alkoxylate, such as ethoxylate, leads to the breakdown of essential due to the elimination of 1,4-dioxane (cyclization) and ultimately to the transformation of the secondary alcohol in the internal olefin.

Upon receipt of ethoxysulfuron primary alcohol neutralization of Palmyra sulfuric acid should be implemented as soon as possible, because otherwise there will be an elimination Proc. of the oxide of sulfur. This can lead to the destruction ethoxylate chain with simultaneous formation of 1,4-dioxane and shortening ethoxylates fragment or to the ultimate formation of alcohols or olefins, depending on the reaction conditions. In the case of ethoxylates of secondary alcohols and especially with low average number of EO units, i.e. low molecular weight ethoxylates of secondary alcohols, which are obtained by the method of the present invention, it is necessary to avoid excess Lewis acid, i.e. sulfur trioxide, at any stage of the reaction, otherwise depending on the reaction conditions, will produce a significant amount of side products, such as internal olefins, 1,4-dioxane, sulfur trioxide or sulfuric acid. It is assumed that this pre-condition will limit the level of transformation in the sulfation of ethoxylates of secondary alcohols, or do you need to identify an alternate way to solve this problem, inherent in the sulfation of low molecular weight ethoxylates of secondary alcohols using acids (Lewis).

After sulfation liquid reaction mixture can be neutralized using an aqueous solution of alkali metal hydroxide, for example sodium hydroxide or potassium hydroxide, an aqueous alkali earth metal hydroxide such as magnesium hydroxide or calcium hydroxide or the basis of the Oia, as ammonium hydroxide, the hydroxide substituted ammonium, sodium carbonate or potassium bicarbonate. The neutralization reaction can be conducted in a wide range of temperature and pressure. For example, the neutralization reaction can be conducted at a temperature in the range from 0 to 65°C and an absolute pressure in the range from 100 to 200 kPa. The time of neutralization may be from 0.5 hours to 1 hour, but if necessary it is possible to conduct the reaction for more or less time.

Hereinafter the present invention will be illustrated by examples which are in no way intended to limit the scope of the invention.

EXAMPLES

(i) Obtaining catalyst

Catalyst 1

Monohydrate calcium acetate (5.5 g) (purity 99%, purchased from the firm Aldrich) at room temperature and atmospheric pressure was added to 23 ml of isopropyl alcohol (IPA purity PA, purchased from Merck). In this mixture with vigorous stirring with a magnetic stirrer, were introduced approximately 0.8 ml of concentrated sulfuric acid (95-97%, purchased from Merck), such a rate that the temperature remained below 40°C. After this mixture was a milky-white suspension was stirred for another 30 minutes and then directly used as a catalyst for joining Ala is lanoxine ("Catalyst 1").

Catalyst 2

Monohydrate calcium acetate (5.5 g) (purity 99%, purchased from the firm Aldrich) at room temperature and atmospheric pressure was added to 23 ml of isopropyl alcohol (IPA purity PA, purchased from Merck). In this mixture with vigorous stirring with a magnetic stirrer, were introduced approximately 0.8 ml of concentrated sulfuric acid (95-97%, purchased from Merck), to which was added 0.55 wt.% of ammonium persulfate (purchased from the firm Aldrich) with such speed that the temperature remained below 40°C. After this mixture was a milky-white suspension was stirred for another 30 minutes and then directly used as a catalyst for joining accelerated ("Catalyst 2").

(ii) Acetoxysilane

Although in examples 1 and 2 were acetoxysilane α-olefins, and not the corresponding internal olefins, C12, specialist in the art will understand that the same essential products could be obtained using such internal olefins.

EXAMPLE 1 (Acetoxysilane 1-dodecane)

1-dodecan (77,2 g, 0.46 mol) and 55.4 g of acetic acid were placed in a round bottom flask. The mixture was heated at 120°C in an oil bath. After the mixture became clear, was added 0.4 ml of H2SO4. A mixture of fast Pribram who stayed in a brown solution. The mixture was left to undergo reaction at 33 hours. After cooling to room temperature the mixture was extracted with water to remove acetic acid and catalyst. The organic layer was analyzed by GC and NMR (see Table 1 for the consultation NMR). These analyses showed that the mixture consisted of 35% wt./mass. of ester (mostly 2-dodecylamine and small amounts of 3-dodecylamino) and 65 wt./wt.% unreacted 1-dodecane and the products of its isomerization to another location of the double bond. This mixture was used as is without any further purification, for experiment ethoxycarbonyl described in example 4.

Table 1
Data of NMR for 2-dodecylamino
1H-NMR (300 MHz, CDCl3)13C-NMR (300 MHz, CDCl3)
The symbol in the formulaδ (ppm)The symbol in the formulaδ (ppm)
Aof 0.9 (3H, t) A14,0
b-i1,3 (16H, m)B22,9
C32,2
d-h29,6-29,9
I25,7
J1,6 (2H, m)J36,2
Kof 4.9 (1H, m)K71,4
Lof 1.3 (3H, d)L20,2
--M171,0
Nof 2.0 (3H, s)Na 21.5

EXAMPLE 2 (Acetoxysilane 1-dodecane)

In a 500-ml round bottom flask in the order was placed 120,8 g of acetic acid (2 mol), 1.55 g FeCl3(9.5 mmol), 1.45 g triftormetilfullerenov acid, i.e. CF3SO3H (9.7 mmol) and 160,0 g 1-dodecene (0.95 mol). Used reagents were purchased from the Aldrich company, and the shutting down of glacial acetic acid, which was obtained from Merck. The resulting mixture was stirred at 80°C in oil bath for 48 hours. Then the temperature was raised to 100°C and was made to undergo reaction for another 55 hours. In the course of the reaction was sampled and watched the transformation by GC. After the reaction continued for a total of over 103 hours, the mixture was cooled to room temperature and 3 times were extracted with water to remove unreacted acetic acid and catalyst. The result obtained organic layer is brown. GC and NMR analyses showed that the mixture consisted of 33% wt./mass. 2-dodecylamine, 4% wt./mass. 3-dodecylamine and ~57% of the mass./mass. olefins (1-C12= and isomerized C12=)and ~2% wt./mass. hardtechno.

The resulting mixture was subjected to distillation under reduced pressure (2 mbar for 2 hours at 150°C) for maximum possible removal of the unreacted olefins. The remainder consisted of 60% wt./mass. 2-dodecylamine, 6% wt./mass. 3-dodecylamine and ~26% of the mass./mass. C12-olefins.

(iii) Alkoxysilane

Although the following alkoxysilane was performed using the ester product of example 1, a specialist in the art will understand that the following reaction alkoxysilane can be performed similarly using the analogy the ranks of essential product, obtained from the corresponding internal olefin.

EXAMPLE 3 (Propoxyimino 1-dodecylamine)

In a test tube for carrying out reactions under pressure, sold under the trade name “Ace” by Ace Glass Inc., were placed 10 g of dodecylamine (purchased from the firm Aldrich), 0.2 g of catalyst 1 and 0.5 ml of propylene oxide and stirred for 24 hours (3×8 hours) at 180°C by heating on an oil bath. The analysis using the1H-NMR showed that approximately 35% of propylenoxide (PO) has undergone a transformation into a product of accession. The presence of a multiplet at δ=5.0 ppm showed the formation of 2-acetoxypropionyl ether and the introduction of propylene oxide by ester bonds.

EXAMPLE 4 (Amoxilonline product of example 1, i.e. the product of acetoxysilane 1-dodecene)

The mixture of products obtained in example 1 was used as such without any further purification for the following experiment ethoxycarbonyl.

40 g of the above-mentioned mixture of the products of example 1 and 0.82 g of a suspension of the catalyst (catalyst 1) was added to 120 ml autoclave (stainless steel). The autoclave was closed and three times was filled with nitrogen under pressure (gauge pressure 4-5 bars) for removing gas from the empty space of the autoclave, and was heated to 130°C. At 130°C, the autoclave was purged with nitrogen (10-15 l/min) for 30 min to dry the project content. Then the excess pressure in the autoclave was increased up to 5 bars by introducing nitrogen and increased the temperature to 165°C.

At 165°C portions were injected ethylene oxide (at a pressure of 10-25 bar (EO/N2<1 volume/volume)using a piston high-pressure pump, which can be purchased from Teledyne Isco, Inc. For security reasons, each adding EO should not give the concentration in the mixture with nitrogen for more than 50% volume/volume (typically each added portion contains 2-3 g of ethylene oxide). After adding the first portion of ethylene oxide was observed short induction period of approximately 5 minutes. Then started the reaction and the pressure in the autoclave was rapidly decreased. When the pressure has stabilized (after 15-20 minutes), has introduced the next portion of ethylene oxide. The new batch was injected until then, until it was completed just add the desired amount of ethylene oxide (39,0 g).

After adding all of the ethylene oxide, the reaction gave a pass for an additional 30 minutes to interacting joined the rest of EO. After that, the autoclave was cooled to 80°C and at this temperature the contents were purged with nitrogen for 20 minutes to remove the last traces of dissolved free of ethylene oxide, and then opened the autoclave. Following this, the temperature was lowered to room, to which the returns to be able to safely remove the mixture of reaction products.

A large part of the mixture did not change their appearance (brown liquid), however, a small portion (approximately 5-10% of the total product) has turned into a not-quite-white sticky solid. In accordance with the mass balance and GC data of the mixture of products some of ethylene oxide (EO) entered into reaction. Using spectroscopy1H-NMR (CDCl3, 300 MHz) it was confirmed that no white sticky solid is the product of the joining EO to second-dodecylamino, as was detected characteristic signal fragment-CH2-located next to the slice-O(C=O)CH3at 4.2 ppm (position A in Fig. 1). This structure confirmed data analysis LC-MS.

Fig. 1: the Product is the inclusion of EO in second-dodecalactam

1. The way to obtain acylated alkoxylate secondary alcohol of the formula (I):

where R1is a linear or branched alkyl group comprising from 1 to 30 carbon atoms, optionally substituted cycloalkyl group comprising from 5 to 30 carbon atoms, or optionally substituted aryl group comprising from 6 to 30 carbon atoms, OA means one or more oxyalkylene fragments, which may be the same or different, n on the mean integer in the range from 0 to 70, and R2is a linear or branched alkyl group comprising from 4 to 32 carbon atoms, optionally substituted cycloalkyl group comprising from 5 to 32 carbon atoms, or optionally substituted bicycloalkyl group including from 7 to 32 carbon atoms, where the method includes:
(i) the interaction of one or more olefins with internal double bonds with one or more carboxylic acids in the presence of a catalytic composition with one or more esters of carboxylic acids;
(ii) the interaction of one or more esters of carboxylic acid, obtained in stage (i)with one or more etkilenecegini reagents in the presence of a catalytically effective amount of a catalytic composition including:
(a) one or more salts of alkaline earth metals and carboxylic acids and/or hydroxycarbonic acids comprising 1-18 carbon atoms, and/or hydrates of the first;
(b) oxygen-containing acid selected from sulfuric acid and phosphoric acid;
(c) an alcohol containing from 1 to 6 carbon atoms and/or ester containing from 2 to 39 carbon atoms;
and/or products of interactions (a), (b) and/or (c)
obtaining one or more acylated alkoxylated secondary alcohols.

2. The method according to claim 1, where Catalytica the Kai song on stage (ii) contains:
(a) one or more salts of alkaline earth metals and carboxylic acids and/or hydroxycarbonic acids containing from 1 to 18 carbon atoms, and/or hydrates of the first;
(b) oxygen-containing acid selected from sulfuric acid and phosphoric acid;
(c) an alcohol containing from 1 to 6 carbon atoms and/or ester containing from 2 to 39 carbon atoms;
(d) peroxynitrate and/or its salt;
and/or products of interactions (a), (b), (c) and/or (d).

3. The method according to claim 2, where peroxynitrate in catalytic compositions for the stage (ii) is selected from peroxycarbonates acid, perhalogenated acid, hypogeogenous acid, peregrinos acid, perarnau acid, Pervozvanny acid and nadkarni acid and/or salt peroxyacids in catalytic compositions for the stage (ii) is selected from ammonium salts, salts of alkaline and alkaline earth metals.

4. The method according to any one of claims 1 to 3, where the salt of alkaline earth metal (a) in the catalytic compositions for the stage (ii) is selected from calcium salts of carboxylic and/or hydroxycarbonic acids and/or hydrates of the former.

5. The method according to any one of claims 1 to 3, where the catalytic composition for stage (i) includes:
(a) at least one compound of the metal, where the specified metal selected from iron, cobalt and Nickel; and
(b) acidic compounds.

6. The method according to claim 5, where the acid compound selected is C acid Bronsted or metal salt and triftormetilfullerenov acid.

7. The method according to any one of claims 1 to 3, where the internal olefins selected from olefins containing from 8 to 32 carbon atoms.

8. The method according to any one of claims 1 to 3, where one or more alkalinizing reagents selected from ethylene oxide, propylene oxide and/or butilenica.

9. The method of producing alkoxylated secondary alcohols, which includes stages:
- one or more acylated alkoxylated secondary alcohols at stages (i) and (ii) of the method according to any one of claims 1 to 3; and
(iii) hydrolysis or transesterification of one or more acylated alkoxylated secondary alcohols to obtain one or more alkoxylated secondary alcohols.

10. The method of producing alkoxylated secondary alcohols, which includes stages:
- get alkoxylated secondary alcohols by the method according to claim 9; and
- sulfation of alkoxylated secondary alcohols.



 

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