A mixture of branched primary alcohols, methods of obtaining, a mixture of biodegradable detergents, washing composition

 

(57) Abstract:

The invention relates to a mixture of branched primary alcohols from C11to C36and to mix them sulfates, alkoxylated, alkoxylates and carboxylates, which have high washing ability in cold water and good biological degradability. A mixture of branched primary alcohols is the average number of side chains on the main chain from 0.7 to 3.0, and has at least 8 carbon atoms and includes methyl and ethyl side chains. The mixture may also contain alcohols having less than 0.5 at. % of Quaternary carbon atoms and less than 5% linear alcohols, at least 40% of methyl side chains. The retrieval method includes a skeletal isomerization of the initial olefin having at least 7 carbon atoms, or dimerization WITH6-C10the olefin with the subsequent conversion of the alcohol or hydroformylation. Subsequent sulfation, alkoxysilane or combining both methods leads to the production of detergent surfactants. Catalysts skeletal isomerization include zeolites having at least one channel with crystallographically free diameter along the X Il is a combination of Nickel chelate with alkylolamides. Washing composition includes one or more substances selected from the group: alkoxylate, primary alkyl sulphates or alkoxysilane primary alkyl sulphates derived from branched primary alcohols, as well as supplements. Washing composition is either granulated detergent or washing up liquid or soap or detergent. The technical result - expanding range of quality detergents. 7 C. and 14 C.p. f-crystals, 7 PL.

The invention relates to new compositions of primary alcohols and their alkoxylates, sulfates and alkoxylates, their preparation and use.

Alcohols olefins with long chain, especially those which have from 10 to 28 carbon atoms, are of considerable commercial importance in many applications, including detergents, Soaps, surfactants and additives, reducing the pour point of lubricating oils. These alcohols receive in accordance with one or more commercial methods, such as oxo or hydroformylation olefins with a long chain. Normal alcohols with long-chain are available NEODOL alcohols from Shell Chemical Company, alcohol EXXAL from EXXON Chemical and alcohols LIAL from Enichem (NEODOL, EXXAL hydroformylation by reacting carbon monoxide and hydrogen with an olefin in the presence of oxobutanoate with obtaining alcohol. The resulting alcoholic composition comprises more than 80% linear primary alcohols from the total amount of alcohols. Side-chain branched primary alcohols included in the composition are mostly carbon atom WITH2in relation to the carrying hydroxyl group to the carbon atom. These alcohols can consistently be converted into anionic or non-ionic detergents or basic surfactants sulphurization or ethoxycarbonyl, respectively, of alcohol. As anionic surfactants for detergents known alcohol-amoxicullin.

A series of NEODOL alcohols has significant commercial success in the production of detergents, since the composition of NEODOL alcohols can be economically obtained with a high yield of linear alcohols. In the manufacture of detergents varieties of surface-active substances it is desirable to use a linear alcohols as intermediates, as it is widely known that linear alcohols biodegradable, while the sulfonates of alcohols with long branched chain have poor biological degradability. As detergents and Soaps used by consumers for washing, in the end, the detergent, which has a good biological degradability.

For example, in U.S. patent 5112519 describes a method for surface active agents by oligomerization WITH3and C4olefins using surface Deaktivierung catalyst ZSM-23 with obtaining oligomers, followed by hydroformylation oligomer and the selection of the composition of semilinear alcohol having less than 1.4 methyl side chains and branching is limited to methyl side chains. Alcohol can be amoxillian and/or sulfated and indicated that he is biodegradable and, moreover, has improved low-temperature properties compared to isotridecyl alcohol. Maintaining the linearity of the composition of the alcohol is less than 1.4 together with the receipt of methyl side chains is important to obtain biodegradable surfactants. It is desirable, however, to obtain a biodegradable surfactant without limitation branching methyl side chains, without limitation branching less than 1.4 and not limited to use as a catalyst surface deactivated katalizatoramisikkativami, using zeolite catalysts that are expensive and can consulates or quickly used when you want to build a long chain with the participation of the catalyst.

Another product, EXXAL 13, obtained by oligomerization of propylene in the presence of an acid catalyst to obtain a wide range of monoolefins from which monoolefinic, with the average number of carbon atoms 13, distilled, but it contains some olefins number of C10-15. The olefin is then subjected to hydroformylation using oxazines. EXXAL 13, as described, is 3-4 methylresorufin tridesilon alcohol, which is used in the lubricating substances and in such detergent compositions which do not require rapid biological decomposition, as EXXAL 13 slowly biodegradable. Although such a large number of side chains is not necessary, it would be desirable to obtain a surface-active substance having a higher number of side chains, which contributes detergency, which, however, easily biodegradable.

In U.S. patent 5196625 described method of dimerization to obtain a linear and/or mooretwin10-C28olefins using catalysts dime is About using demonizovana olefins to obtain alcohols were not mentioned. Further, in the patent indicate that is commonly known that linear and mooretwin the alkylaromatic sulfonates are usually more easily biodegradable than multiresistant the alkylaromatic sulfonates and therefore more desirable as detergents". This explains that in this patent the resulting olefins are mainly linear and nanorazmernymi. Again, it is desirable to obtain highly branched products that have good washing ability and easily biologically degradable, from alcohols and also have no significant restrictions on the number of side chains.

In U.S. patent 4670606 also recommended to use "linear detergent otsopirtti or those compounds, in which the linear fraction as high as possible to obtain a detergent with a good biological degradability, while otsopirtti, which are very extensive, it is desirable to use as additives in lubricating oils, as branched alcohols reduce the pour point of lubricating oils. Thus, this invention relates to methods for selecting these two forms of the mixture.

The desire to obtain highly branched is alcolici when hydroformylating olefins using cobalt carbonyl catalyst, in this patent it is noted that in this way we obtain a composition, which contains a branched connection, if the original materials are internal olefins, which are particularly undesirable because of their low biological decomposing. Therefore, in this patent it is recommended to use catalytic processes under which receive a mixture having a high ratio of linear/branched compounds.

As noted earlier, a number of strongly branched linear NEODOL alcohols, intermediates for getting detergent surfactants is commercially successful, partly because of their high degree of linearity makes them easily biodegradable. However, the high degree of linearity also increases the hydrophobicity of hydrophobic side chains, thus lowering the ability of such compounds to dissolve in cold water/detergent capacity. In General, wysokowydajny sulfates of alcohols show poor solubility in cold water/detergent capacity. Together with the use of biologically degradable compounds existing rules also recommend lowering the washing temperature.

Therefore, there is an increasing need for detergents at low temperatures. The solution to this problem is not simply to increase the number of side chains of higher olefinic alcohol to reduce hydrophobicity and thereby successfully improving detergency in cold water, because, as noted above, it is well known that branched compounds show poor biological degradability.

The present invention is the creation of new mixtures of branched primary alcohols and their alkoxylates, sulfates and alkoxylated derivatives that meet the requirements for biological decomposing and detergency in cold water, and methods of obtaining these compounds.

The invention therefore firstly relates to mixtures of branched primary alcohols having from 11 to 36 carbon atoms and an average branching molecule from 0.7 to 3.0, and specified branches contains methyl and ethyl side chains.

Secondly, the invention relates to a method for the specified composition of branched primary alcohols, which involves the following stages:

a) contacting the source of the olefin containing linear olefins having at least 7 carbon atoms with the catalyst is the same number of carbon atoms; and

b) the conversion of the specified branched olefin in this mixture of primary alcohols.

The term "skeletal isomerization" in this case means a hydrocarbon isomerization, in which the direct chain turn, at least partially, in branched chains with the same number of carbon atoms. The catalyst of stage a) is preferably a zeolite having at least one channel with crystallographically free diameter in the range from 0.42 to 0.70 nm. The conversion of alcohol at the stage b) is preferably carried hydroformylation.

Thirdly, the invention relates to various methods of obtaining the above mixtures of branched primary alcohols having from 13 to 21 carbon atoms, which include the following stages:

(a) dimerization in the presence of a homogeneous catalyst for the dimerization, the original olefin containing FROM6-C10olefin, obtaining C12-C20branched olefin; and

b) convert the specified C12-C20a branched-chain olefin in the specified mixture of branched primary alcohols.

The original olefin at the stage a) is preferably a linear olefin and preferably contains Kreisel. Homogeneous catalyst preferably contains a mixture of carboxylate Nickel or Nickel chelate with alkylhalogenide or alkylamidoamines. Optional branched olefin obtained in stage a) is subjected to isomerization of the double bond before carrying out stage b). The transformation of the alcohol at the stage b) is preferably carried hydroformylation.

Fourth, this invention relates to a mixture of alkoxylated branched primary alcohols obtained by the interaction of the specified composition of the branched primary alcohol with ethylene oxide (oxirane).

Fifthly, the invention relates to branched primary alkylsulfate obtained by sulfation of this mixture of branched primary alcohols.

And Sixthly, the invention relates to detergent compositions, including:

a) one or more surfactants selected from the group specified alkoxylated branched primary alcohol branched primary alkyl sulphates and branched alkoxycarbonyl primary alkyl sulphates;

b) modifying additive; and

c) optionally one or more target components selected from the group comprising controlling Diviziya supplements hydrotropic and stabilizers.

In this description, the phrase "the average number of side chains in chain molecules" means the average number of side chains in the molecule of alcohol, measured by using13Nuclear magnetic resonance (13With NMR), as described below. The average number of carbon atoms in the chain determined by gas chromatography.

In this description and the formula have been made various references to the percentage of the side chains in this position carbon, the percentage of side chains on the basis of the types of side chains, the average number of side chains and the percentage of Quaternary atoms. These values were measured and determined using a combination of the following three methods 13WITH NMR.

(1) the First method is a standard method with a back-frame, in which the peak13Equal to 45 degrees and the delay time of recycling is 10 (agent relaxation organic free radical are added to a solution of branched alcohol in deuterated chloroform to guarantee quality results). (2) the Second method is a method of J-Modulated Spin Echo NMR (JMSE), in which the delay time is 1/J is equal to 8 MS (J is equal to 125 Hz and is a constant combination between carbon and proton for these aliphatic, having an even number of protons, for example CH3/CH from CH2/Cq(Cqis Quaternary carbon). (3) the Third method is a method of JMSE NMR "quat-only", in which the delay time is 1/2J is equal to 4 MS, and which gives the spectrum contains signals only from the Quaternary carbon. Methodology JMSE NMR "quat-only" for the determination of Quaternary carbon atoms is sufficiently sensitive to detect the presence of up to 0.3 at.% Quaternary carbon atoms. As an optional extra stage if you want confirmation of the conclusions obtained from the analysis of the results of the spectrum JMSE NMR "quat-only", you can also use the DEPT-135 NMR sequence. Found that the DEPT-135 NMR sequence helps to distinguish these Quaternary carbons from protonated carbon decay. The sequence of the DEPT-135 has this ability, as it gives the spectrum of "opposite" to that obtained using methods JMSE "quat-only". While the latter ignores all signals in addition to signals of Quaternary carbons, DEPT-135 passes only signals of Quaternary carbons. The combination of the two spectra is therefore very useful for the detection of nötsch the data description mean the number or absence of Quaternary carbons determined by the method of JMSE NMR "quat-only". If not necessarily, there is a desire to confirm the results, also use the technique DEPT-135 to confirm the presence and number of Quaternary carbons.

Evaluation of detergency conduct, as used here, based on the standard test for washing powders to high density (SPIT) washing capacity/re-deposition of dirt. Evaluation of the working of the samples was conducted using a methodology labeled atom developed by Shell Chemical Company at the temperature indicated in the table. III at a water hardness of 150 h/m caso3(the molar ratio of CaCl2/Mgd2=3/2). Sulfated compositions of the primary alcohol of the present invention tested in the ratio of 1/4 in relation to contaminated multiscreen sebaceous glands, Tamanskaya and clay constantly compressed 65/35 fiber polyester/cotton (PPE/X). Tested SPIT at a concentration of 0.74 g/l, containing 27 wt.% composition of sulfate primary alcohol, 64 wt.% modifying additives (zeolite 4A) and 27 wt.% sodium carbonate.

Composition radioactiveman polluting multisecret sebaceous glands presented in tabili such to measure ability in cold water at a temperature of 10oWith, and in hot water at a temperature of 36oC. the stirring Speed was 100 rpm Contaminated Radiometrie sample 4" x 4" washed Terg-O-Tometer, they were washed by hand. Water from the wash and rinse were combined to determine the removal of contaminants by the secretion of sebaceous glands. The specimens were examined to determine the removal of clay.

Detailed descriptions of the methods for determining the detergency and radiolabelling techniques can be found in B. E. Gordon, H. Roddewig and W. T. Shebs, HAOCS, 44: 289 (1967), W. T. Shebs and B. E. Gordon, JAOCS, 45:377 (1968) and W. T. Shebs, Radioisotope Techniques in Detergency, Chapter 3, Marcel Dekker, New York (1987).

The methods for testing biological degradation for the determination of Biodegradability are working examples of sulfates were performed according to the testing methods presented in 40 CFR 796.3200, also known as the test method OECD 301D. Under a biodegradable mixture of sulfates of primary alcohols or surfactants is meant that the compound or the mixture of give-defined biochemical oxygen demand (BOD), equal to 60% or more for 28 days, and this level should be achieved within tenia has an average chain length of the molecule in the range from 11 to 36 carbon atoms. For many applications of surface-active substances, such as detergents, a mixture of alcohols has an average chain length 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or 21 carbon atom, or any intermediate decimal fraction, expressed as an average in the range from 11 to 21 carbon atoms. The number of carbon atoms includes the carbon atoms along the Foundation chain, and the carbon atoms of the side chains.

Preferably at least 75 wt.%, more preferably at least 90 wt.% molecules in a mixture of primary alcohols have a chain length of 11 to 21, more preferably from 14 to 18 carbon atoms. One of the features of this invention, as defined and set out above, is the average number of side chains comprising at least 0,7. The mixture, with the average number of side chains of at least 1.5, in particular from 1.5 to 2.3, especially from 1.7 to 2.1, achieve a good balance detergency in cold water and the extent of biological degradation during sulfation. Normal sulfates linear alcohols contain the average number of side chains only from 0.05 to 0.4 and fully biodegradable. To date, however, the introduction of a greater degree of branching to improve morenew. A mixture of primary alcohols of this invention when the sulfation have the advantage in the introduction of a larger number of side chains to improve their detergent properties in cold water without deterioration of Biodegradability. Detergent properties in cold water was improved when the number of the side chains comprising at least 1.5.

A feature of this invention is to obtain a mixture of primary alcohols, as described above, with less than 0.5 at.% WITHThurthat measured using modified methods quat only JMSE13C-NMR, with a limit of detection of 0.3 at. % or above, and the preferred mixture of primary alcohols which contain noThurthat measured by the NMR technique. For reasons not quite clear, I believe that the presence of CThurin the molecule of alcohol interferes with the biological decomposition of this specific sulfated molecules using biological organisms. It was found that alcohols containing not less than 1 at.% WITHThurhave a low Biodegradability. Also believe that previous attempts to introduce a high degree of branching resulted in the formation of such a number WITHeven the ante of this invention is less than 5%, or more preferably less than 3% of the molecules of alcohol in the mixture of primary alcohols are linear alcohols. To effectively reduce the number of linear alcohols to such a small amount in the mixture was obtained by introduction of branching in the olefin feedstock using methods skeletal isomerization or dimerization using effective catalysts, as described below, unlike the introduction of the side chains using techniques such as the oligomerization of propylene molecules using acidic catalysts or oligomerization using a zeolite catalyst. In a more preferred embodiment, the mixture of primary alcohols contain less than 3% linear alcohols. The percentage of linear molecules can be determined using gas chromatography.

If branching is achieved by skeletal isomerization, a mixture of primary alcohols of this invention may be characterized using NMR techniques as having from 5 to 25% branches in C2the position of the carbon relative to the hydroxyl carbon atom. In a more preferred embodiment, from 10 to 20% of the side chains are in C2position, which is determined by the NMR technique. The mixture of primary alcohols also usually has from 10% to 50% of the side chains in the C3position, more typically from 15% to 30% of in3position, which also determine the position get that mixture of primary alcohols contains a significant number of side chains in the C2and C3the provisions of the carbon.

Using NMR techniques, it was found that a mixture of primary alcohols not only has a significant number of side chains in the C2and C3the provisions, but also the fact that many of the composition of the primary alcohol have at least 5% of the side chains in the form of a terminal isopropyl, that means a methyl side chain in the second and last positions of the carbon skeleton of the chain relative to the hydroxyl carbon. It was discovered at least 10% of the side chains in the form of a leaf in a mixture of isopropyl primary alcohols, usually in the range from 10% to 20%. In normal hydroformylating the olefins number of NEODOL less than 1% and usually 0,0% side chains are the side chains in the form of a terminal isopropyl. However, received with the help of skeletal isomerization of olefins, a mixture of primary alcohols according to this invention contains a high percentage of side chains in the form of end-isopropyl relative to the total number of side chains.

Given the total number of side chains, available in2WITH3and isopropyl provisions, there are variants of the present invention, in to the of the invention, however, includes all side chains present on the main carbon chain. In another preferred embodiment of the present invention, the total number of methyl side chains is at least 40%, even at least 50% of the total number of side chains that are measured by the NMR technique described above. This percentage includes the total number of methyl side chains, shown using NMR techniques described above, C1-C3the provisions of the carbon relative to the hydroxyl group and a methyl side chain in the form of isopropyl at the end.

It is noteworthy that consistently found that the amount of ethyl side chains exceeds the number of ethyl side chains in the NEODOL alcohols. The amount of ethyl side chains may be in the range from 5% to 30%, more typically from 10% to 20% in relation to all types of side chains that are determined by the method of NMR. Thus, the skeletal isomerization of olefins gives as methyl and ethyl side chains, and these alcohols when the sulfation alkoxysilane or both methods give very good performance when tested on the biological degradability and ability. Thus, the types of catalysts, cumetidine side chains. I believe that the presence of different types of side chains improves the overall balance of properties.

The olefins used as the source of olefinic raw materials for the skeletal isomerization are at least10monoolefins. In a preferred embodiment, olefin feedstock contains10-C35monoolefinic. Olefins range FROM11-C19are preferred for use in this invention for obtaining mixtures of primary alcohols of the number of C12-C20that are most commonly used for detergents. As a General rule, the higher the number of carbon atoms in the derived surfactants, the better its physical properties and its ability to formulate in the form of various preparative forms.

In General, the olefins in the olefin composition of raw materials are mostly linear. Attempts to use raw materials with a predominantly branched olefins containing Quaternary carbon atoms or an extremely long side chains, result in the need to use methods of separation after the transmission of a stream of olefin through a layer of catalyst to separate these species from the desired Razumov, the original olefinic raw materials, prepared for skeletal isomerization, preferably contains more than about 50%, more preferably more than about 70% and most preferably more than about 80% or more molecules of linear olefins.

Olefinic feedstock is not usually consists of 100% olefin, having a specific carbon chain length, as this purity is not commercially available. Olefinic feedstock is typically a distribution of monoolefins with different carbon chain length, with at least 50 wt.% olefins having a specific carbon chain length. Preferably, the olefin feedstock contains more than 70 wt.%, more preferably about 80 wt.% or more monoolefins having a specific carbon chain length (for example, C7-C9C10-C12WITH11-C15C12-C13C15-C18and so on), the remainder of the product is an olefin with a different number of atoms of carbon or other carbon structure, diolefine, paraffins, aromatic compounds and other impurities resulting from the synthesis. The location of the double bond is not limited. A mixture of olefinic feedstock can S="ptx2">

Products Chevron Alpha Olefin (trademark of Chevron Chemical Co.) mostly produced as a linear olefins by cracking of paraffin. Commercial products of olefin obtained by the oligomerization of ethylene, sold in the United States by the company Shell Chemical Company under the trademark NEODENE and company Ethyl Corporation under the trademark of Alpha-Olefins. Certain methods of obtaining the appropriate linear olefins from ethylene are described in U.S. patents 3676523, 3686351, 3737475, 3825615 and 4020121. Although the majority of such olefinic products contain mostly alpha-olefins, linear internal olefins with a long chain, are also produced commercially, for example, by chlorination-dehydrochlorination of paraffins, dehydrogenation of paraffin and isomerization of alpha-olefins. Products of linear internal olefins with a chain length8-C22sold by Shell Chemical Company and Liquichemia Company.

The catalyst used for the skeletal isomerization, preferably contains a zeolite having at least one channel with crystallographically free diameter in the range from 0.42 to 0.70 nm, measured at room temperature, and has virtually no channels that have a free diameter greater than 0,70 nanometers.

The catalyst for the skeletal isomerization proved interval. The catalyst should not have a diameter at the entrance of the channel, exceeding 0,70 nanometers above the specified limits. Zeolites having diameters of channels is greater than 0.7 nm, prone flavoring, oligomerization, alkylation, coking and formation of by-products. On the other hand, if the zeolite does not contain channels having free diameters along the X or Y planes, at least at 0.42 nm, channel size becomes too small to ensure the diffusion of the olefin into the channel and out of it as soon as the olefin becomes branched. Thus, the zeolite must have at least one channel having a free diameter in the range from 0.42 to 0.7 nm. All other requirements are preferred.

Suppose that a molecule of olefin, due to its considerable length of the carbon chain, can not enter the channel of the zeolite, to diffuse through and emerge on the other side of the channel. The degree of divergence observed by passing the feedstock olefins over zeolite that does not match theoretical degree of branching if each molecule of olefin passed through the channels. However, I believe that most of olefins partially penetrate into the channel at a distance, eff this case, molecules of olefin in the composition will preferably have the structure, which is branched at the ends of the carbon chain of the olefin and is essentially linear in the middle of the molecule, i.e. at least 25% of the carbon atoms in the middle of the molecule are unbranched. The scope of this invention, however, includes a fork anywhere along the main carbon chain that meets the above parameters regarding the structure of a molecule.

The preferred options for the structure of zeolite is described in U.S. patent 5510306. The structure of the zeolite is also described in Atlas of Zeolite Structure Types by W. M. Meier and D. H. Olson. Regarding the structure in the preferred embodiment, the catalyst has a TV with free diameters in the range of from more than 0,42 nm to less than 0,70 nm in X and Y planes in the [001]. Zeolites with such specific dimensions of the channels is usually called zeolites with medium or intermediate channels and typically have 10-T-membered (or corrugated 12-T-membered) ring structure of the channel on one side and 9-T-membered or less (small pores) on the other hand, if any. The number of channels in the zeolite and their direction (parallel, mesoeconomic between a crossing or connected at any angle) is unlimited. Also unlimited size have a free diameter or X, or Y planes more than 0,70 nm. For example, other channels having free diameters of 0.42 nm or less in one or both X and Y planes, are included in the scope of this invention.

Also unlimited number of dimensions, one, two or three, which may have a system of channels. As the scope of the present invention includes a two - or three-dimensional zeolites with interconnected channels with any size of less than 0,70 nm and including at least one channel with the specified size may be limiting the circumstances in which, for example, the olefins can meet at the intersection of interconnected channels and timeresults or oligomerizate depending on the size of the olefin, the proximity of the connecting intersections to the output of the channel, the size of the connecting intersections, temperature and flow rate, among other factors. Although it is not desirable that this dimer could diffuse back out of the zeolite, the dimer can coking the catalyst or tear the inside of the channel structure, forming by-products - olefins having side chains with Quaternary carbon atom. Thus, the system of interconnected channels in two - or three-dimensional zeolite species data process conditions, breaking that can form Quaternary branched by-products. In the preferred embodiment, all channels connected to the channel with the specified sizes are available diameters in X and Y planes of 0.42 nm or less to prevent the possibility of contact with each other two olefin molecules inside the zeolite and the dimerization and trimerization. This preference, however, only applies to interconnected channels. The zeolite containing more than one channel, one-, two - or three-dimensional or even overlapping in different planes, but not connected, will not increase the possibility of dimerization or trimerization, since the channels are not linked. Thus, for these types of structures preferences no, unless they meet the basic requirements listed above.

Examples of zeolites, including the molecular sieves, which can be used in the methods of the present invention, the channel size in the range from 0.42 to 0.70 nm, include ferrierite, AlPO-31, SAPO-11, SAPO-31, SAPO-41, FU-9, NU-10, NU-23, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, SUZ-4A, MeAPO-11, MeAPO-31, MeAPO-41, MeAPSO-11, MeAPSO-31, and MeAPSO-41, MeAPSO-46, ELAPO-11, ELAPO-31, ELAPO-41, ELAPSO-11, ELAPSO-31, and ELAPSO-41, lamonta, cancrinite, offretite, hydrogen form stilbite,mi names, are considered equivalent. Review the description of the compositions of most of these zeolites are presented in New Developments of Zeolite Science Technology, "Aluminophosphate Molecular Sieves and the Periodic Table", Flanigen et al. (Kodansha Ltd., Tokyo, Japan 1986).

Many natural zeolites, such as ferrierite, gelandet and stilbite have a one-dimensional porous structure with a pore size equal to or slightly smaller than approx 0.42 nm in diameter. These same zeolites can be converted into zeolites with the desired large size of the channels by removing the associated alkali metals or alkaline-earth metals by methods known to the person skilled in the art, such as exchange with ammonium ion, optionally followed by calcination, to obtain the zeolite is essentially in its hydrogen form. See, for example, U.S. patent 4795623 and 4942027. Replacement associated alkaline or alkaline-earth metal hydrogen increases the diameter of the channels. It is clear that the diameter or size of the channel means the diameter or size of the channel, is effective for diffusion. In the alternative case of natural zeolites, having too large of a channel, such as some forms of mordenite can be changed by replacement of the alkali metal ions with large razmernostyu for methods of this invention.

Particularly preferred zeolites are those that have ferrierite isotype frame structure (or homeothermy). See Atlas of Zeolite Structure Types by W. M. Meier and D. H. Olson, published by Butterworth-Heinemann, third revised edition, 1992, page 98. Prominent structural features of ferrierite detected using x-ray crystallography, are parallel channels in the aluminosilicate framework, which is almost elliptical in cross section. Examples of such zeolites having ferrierite isotype frame structure include natural and synthetic ferrierite (can be orthorhombic or monoclinically), Sr-D, FU-9 (EP-55529), ISI-6 (U. S. Pat. No. 4578259), NU-23 (EP-103981), ZSM-35 (U. S. Pat. No. 4016245) and ZSM-38 (U. S. Pat. No. 4375573). The hydrogen form of ferrierite (N-ferrierite) is the most preferred zeolite and is essentially one-dimensional, having parallel spaced channels with elliptical channels having free diameters of 0.42 x 0,54 nm in the X and Y planes in the [001], which are large enough to allow entrance of a linear olefin and diffusion from or through the channel of isoolefine with methyl side chains and small enough to slow the Sabbath.

The catalyst for the skeletal isomerization used in the isomerization processes of this invention may be combined with the refractory oxide, which serves as a binding material. Suitable refractory oxides include natural clays, such as bentonite, montmorillonite, attapulgite and kaolin; alumina; silica, alumina-silica; gidrirovannoe aluminum oxide; titanium dioxide; zirconium dioxide and mixtures thereof. The weight ratio of zeolite and binder material is in the range from about 10: 90 to about 99.5:0.5, preferably from about 75:25 to about 99:1, more preferably from about 80:20 to about 98:2 and most preferably from about 85:15 to about 95:5 (anhydrous basis).

Preferably, the binding material, for example, be chosen from silica, alumina, silica-alumina and clay. The most preferred binding material are aluminum oxide, such as pseudoboehmite, gamma and bayerite oxides of aluminum. These binding materials are easily commercially available and used for preparation of catalysts based on aluminium oxide. The series of oxides of aluminum VERSAL from LaRoche Chemicals and the series of oxides of aluminum CATAPAL from Vista Chemical Company before the materials upon receipt of these catalysts (VERSAL and CATAPAL are trademarks). Preferred binding materials based on aluminum oxide used in the preparation of the catalyst, especially when using extrusion, are finely dispersed powders of aluminum oxide. Such highly dispersed aluminum oxide have a particle size of more than 50% in aqueous acid dispersion with a content of acid 0.4 mg equivalents of acid (acetic acid) per gram of Al2O3. Such highly dispersed aluminum oxide represented by alumina Vista's CATAPAL d

Preferably the catalyst skeletal isomerization also receive at least one acid selected from monocarboxylic acids and inorganic acids and at least one organic acid with at least two carboxylic acid groups ("polycarboxylic acid"). Preferred monocarboxylic acid include monocarboxylic acid having a substituted or unsubstituted hydrocarbonous (hydrocarbon) group, having from 1 to 20 carbon atoms, which may be aliphatic, cyclic or aromatic. Examples include acetic acid, formic acid, propionic acid, butyric acid, Caproic acid, glycolic acid, lactic acid, hydroxybutiric KIS is islote. Preferred inorganic acids include mineral acids such as nitric acid, phosphoric acid, sulfuric acid and hydrochloric acid.

The preferred polycarboxylic acid is an organic acid with two or more carboxylic acid groups attached through a bond carbon-carbon hydrocarbon moiety. Communication can be in any part of the hydrocarbon residue. Polycarboxylic acid preferably has a hydrocarbon portion having 0 to 10 carbon atoms, which may be aliphatic, cyclic or aromatic. The hydrocarbon portion has 0 carbon atoms for oxalic acid with two carboxylic acid groups attached through a bond of carbon-carbon. Examples of polycarboxylic acids include, for example, tartaric acid, citric acid, malic acid, oxalic acid, adipic acid, malonic acid, galactarate acid, 1,2-cyclopentane dicarboxylic acid, maleic acid, fumaric acid, taconova acid, phthalic acid, terephthalic acid, phenylmalonate acid, gidroksiflavona acid, dihydroxyfumaric acid, tricarballylic acid, benzene-1,3,5-tricarboxylic customerone the above acids or any streamerone the above acids. Polycarboxylic acids with at least two carboxylic acid groups and at least one hydroxyl group is more preferable. The most preferred secondary acid (i.e., polycarboxylic acids are acetic acid, tartaric acid and malic acid.

Optional, metals, activating the oxidation of coke, can be introduced into the catalysts of the present invention to activate the oxidation of coke in the presence of oxygen at temperatures greater than about 250oC. because the term "metal(s)" used here in relation to the oxidation catalysts, these metals are not necessarily in the zero oxidation state and in many cases are in the highest oxidation state. Thus, the term "metal(s)" may include both oxides and metals. Preferred used metals, activating the oxidation of coke, are transient and rare earth metals. More preferably metals, activating the oxidation of coke are selected from groups IB, VB, VIB, VIIB and VIII of the series of transition metals of the Periodic table. Especially preferred are Pd, Pt, Ni, Co, Mn, Hell, and SG. Most preferred are metals of group VIII is palladium and/or platinum is the catalyst. When using platinum and/or palladium are preferred rather smaller than the large quantities of metals introduced into the zeolite/binding material. Preferably platinum and/or palladium ranges from 5 to 3000 hours/million by weight. with respect to the total weight of the final catalyst.

In a preferred embodiment, the catalysts of this invention can be obtained by mixing a mixture of at least one zeolite defined above, bonding material containing aluminum oxide, water, at least one monocarboxylic acid or inorganic acid and at least one polycarboxylic acid in a vessel or container with obtaining pellet mixed mixture, and calcining the pellets at elevated temperatures. In one preferred embodiment, the zeolite powder and the powder containing alumina is mixed with water and one or more monocarboxylic acid or inorganic acid (first acid) and one or more polycarboxylic acid (second acid) and optionally one or more metal connection, activating the oxidation of coke, and the resulting mixture (paste) formed into granules. Alternatively, the mixture can be impregnate metal, activating okidaitojima used form of hydrostatic or mechanical pressing with

obtaining a matrix or form. During extrusion may not necessarily be used extrusion additives, such as derivatives of cellulose, such as METHOCEL F4M the hypromellose (METHOCEL is a trademark) (manufactured by The Dow Chemical Company). The term "cake" in this case can mean any shape or form as long as the materials are in consolidated form. The resulting pellet calicivirus at a temperature in the range from the lower limit from 200oC, preferably from 300oS, more preferably from 450oWith up to a upper limit to 700oWith, preferably up to 600oS, more preferably up to 525oC.

The first acid, the second acid is preferably in the range from 1: 60 to 60:1, more preferably from 1:10 to 10:1. The first acid is used in amounts effective for peptization of the mixture. Preferably the amount of the first acid is from 0.1 to 6 wt. %, more preferably from 0.5 to about 4 wt.% with respect to the total weight of zeolite and containing aluminum oxide binding material (anhydrous solid basis). Aluminum oxide having a lower dispersion than Vista CATAPAL D, may require great is I catalytic activity of the catalyst, that is from 0.1 to 6, preferably from 0.2 to 4 wt.% with respect to the total weight of zeolite and containing aluminum oxide binding material (anhydrous solid base).

The mixture is stirred thoroughly or vigorously until it becomes homogeneous. The stirring can be performed by combining all of the components of the mixture simultaneously or adding mixture components at various stages of mixing. Mixing can be accomplished by pasteurianum. The term "pasteursvej" in this case means the mixing of powders, to which water is added in a quantity sufficient for the formation of a thick paste, and where such mixing is accompanied by a grinding paste. Commercially available machines for partobrazovane, such as the Lancaster Mix Muller and Simpson Mix Muller can be used for mixing. Commercial mixers, such as rubber mixer and/or mill to obtain powders can also be used for mixing.

Not necessarily metal, activating the oxidation of coke, can be impregnated in the obtained pellets by impregnation of the metal-containing solution instead of mixing into a paste-like mixture.

The temperature at which the above temperature, when the olefin Criciuma. The appropriate values of pressure supported during isomerization reactions is equal to the partial pressure of the olefin in the range from 10 to 100 kPa, more preferably from about 50 to 500 kPa, most preferably more than 50 to 200 kPa.

High conversion, high selectivity and high yield are the hallmarks of the method of the present invention. The original olefinic feedstock containing linear olefins having on average at least 7 carbon atoms, in contact with a catalyst effective for skeletal isomerization of these linear olefins with a degree of conversion of at least 40% in a single pass. However, the method of this invention enables the skeletal isomerization of linear olefins with a much higher degree of conversion. When carrying out the methods of the present invention in one pass achieved the degree of conversion of at least 70%, preferably at least 80%, more preferably at least 90% and most preferably at least 95%. Mostly this degree of conversion is achieved at temperatures in the range from 200oWith up to 500oC, preferably at temperatures of the tion, also are highly selective in obtaining skeletal-branched-chain isomerized olefins. Although high selectivity is achieved in the process of skeletal isomerization selectivity of the catalyst in the production7or higher branched olefins from linear C7or higher linear olefins is at least 30% in a single pass, while the use of catalysts with lower selectivity is not sufficiently effective or economically feasible. Higher selectivity of at least 70%, more preferably at least 80%, most preferably at least 90% and even as high as at least 95%, is achieved in the process of this invention in a single pass.

Another advantage is obvious when conducting skeletal isomerization stream7or higher olefins according to the method of the present invention is that a high degree of conversion of the flow of linear olefins can be obtained simultaneously with high selectivity in respect of skeletal-branched-chain isomerized olefins. The original olefinic feedstock preferably into at least 70% with selectivity in Oia least 80%, most preferably at least 90%. In another embodiment, becomes at least 80% of the original olefinic feedstock with selectivity against skeletal-branched-chain isomerized olefins of at least 80%, more preferably at a selectivity of at least 90%, most preferably at a selectivity of at least 95%. In yet another variant becomes at least 90% of the olefins with a selectivity of 90% or more in relation to skeletal-branched-chain isomerized olefins, more preferably with a selectivity of 95% or more.

The process of skeletal isomerization also gives a high yield of skeletal-branched-chain isomerized olefins. The output of skeletal-branched-chain isomerized olefin should be at least about 10%, but in practice, the output of at least about 50%, more preferably at least about 65%, most preferably at least about 80% and even up to about 90%. The highest achieved output of skeletal-branched-chain isomerized olefins is limited to the equilibrium concentration of branched olefins at a temperature of skeletal isomerization.

This way the skeletal isomerization can be held is in an hour. Preferably CIOs is from 0.5 to 50, more preferably from 1 to 40, most preferably from 2 to 30 per hour. At low CIOs have the opportunity to carry out the process at low temperatures to achieve high output and skeletal branched-chain isomerized olefins. At high CIOs temperature usually increases to maintain the desired degree of conversion and selectivity in relation to skeletal-branched-chain isomerized olefins. Next, the optimum selectivity is usually achieved at low values of partial pressure of olefin mentioned above. For this reason, it is often preferable to dilute the feedstock dilution gas, such as nitrogen or hydrogen. Although the reduction in the partial pressure of olefin using the dilution may be useful for improving the selectivity of the process, the dilution of the original olefinic feedstock is not required.

When using diluent molar ratio of olefin to the diluent may vary from 0.01: 1 to 100:1 and typically is in the range from 0.1:1 to 5:1.

If branching is achieved by the reaction, the mixture of primary alcohols of this invention has a relatively small number of branching points Esto or no end-ISO-propyl groups, that is a very small number of or no side chains on the second - last carbon atoms along the main chain of the molecule of the alcohol relative to the hydroxyl carbon atom. In particular, a normal molecule of alcohol in this case, contains less than 25% of the side chains in the C2and C3positions and less than 5% of the limit of the isopropyl groups, more typically isopropyl group are not detected.

Because of these provisions of the carbon molecules of the alcohol, obtained from demonizovana olefins such as NEODOL alcohols. However, unlike the NEODOL alcohols, which are predominantly linear, a mixture of primary alcohols of this invention is to average a large number of side chains per molecule. Due to the large number of side chains found in the mixture of primary alcohols of the present invention, and a relatively low percentage of side chains in positions2and C3and regulations carbon end-isopropyl most of the side chains are closer to the center of the molecule, with a considerable number of side chains located on one or both demonizovana carbon atoms. These NMR spectrum was consistent with the data on the position of the side chains, the resulting calculations of the invention, include the following: methyl, ethyl, propyl and butyl, or with a higher number of carbon atoms. A significant number of side chains identified by NMR, was ethyl group, although this can vary depending on the composition of the feedstock and process conditions. In one embodiment, however, the number of ethyl groups in the mixture of primary alcohols of this invention ranged, preferably from 10% to 30%, which significantly exceeded the number of ethyl groups in the NEODOL alcohols. The number of methyl groups defined NMR, also varied widely for the same reasons. Usually, however, the number of methyl groups ranged from 10% to 50% according to NMR.

In General, a mixture of primary alcohols of this invention was obtained by dimerization of olefinic feedstock containing6-C10linear olefins in the presence of a dimerization catalyst under conditions of dimerization with getting C12-C20olefins.

In one embodiment of the invention olefin feedstock contains at least 85 mol.%, preferably at least 90 mol.%, more preferably at least 95 mol.% linear olefins. The rest of olefinic feedstock contained only a small erati olefins with short or long chain. In the preferred embodiment, however, the olefin feedstock contains at least 85 wt.% WITH6-C10olefins, more preferably 90 wt.% and most preferably 95 wt. %6-C10olefins. Another advantage of the method of the present invention is that it is possible to obtain a mixture demonizovana olefins with odd and even number of carbon atoms, using a mixture of olefins with odd and even number of carbon atoms in the feedstock that is different from those processes that are based on the oligomerization or3or4olefins to higher olefins.

Olefinic feedstock can be obtained from internal or alpha-olefins or mixtures thereof. Preferably the majority of the olefins present in the feedstock include internal olefins, as dimerization of these olefins is possible to obtain different types of side chains, i.e. methyl, ethyl and have various side chains, and even butylene side chains. Under the majority's implied that more than 50% of the olefinic feedstock includes internal olefins. More preferably olefinic feedstock contains at least 75 wt.% internal olefins.

2over an iron or cobalt catalyst; that is different from the trimeric and tetramer raw materials3or4olefins, which are strongly branched or require special stage extraction for the arts in the range of from about -10oWith up to 100oC, preferably from 20oWith up to 50oC for 1/2 to 8 hours, preferably from 1 to 5 hours, using a molar ratio of olefin to catalyst of from 200 to 20,000, preferably 1,000 to 10,000 moles of olefin per mole of catalyst. The reaction is usually carried out as a liquid-phase reaction using a pressure in the range from 0 to 300 kPa, preferably from 100 to 200 kPa. If dimerization is conducted as a periodic process, the catalyst may be appropriately prepared in situ in the reactor. The reaction can also be carried out as a continuous, paliperidone or multistage process. It should be clear that where there are common or preferred process conditions (i.e. temperature, time, ratio of catalyst and so on), can be used in other process conditions. The optimal process conditions (i.e. temperature, reaction time, ratio of reagents, catalysts, solvents etc) may differ depending on the specific reagents, catalysts or solvents, but can be determined using conventional optimization techniques. Catalysts for the dimerization of the present invention can be obtained by the interaction of the relevant condo add them in the olefinic feedstock, as this may lead to the destruction of the catalyst. Can be used incremental solvents, such as chlorobenzene or cyclohexane, which does not reduce the efficiency of the catalyst.

The choice of catalyst for the dimerization is based on the definition of the catalyst, selective in obtaining high output demonizovana olefins having on average from 0.7 to 3.0 and preferably from 0.9 to 2.0 side chains in the molecule. These catalysts are preferably soluble in the hydrocarbon medium, for example, the original olefinic feedstock. Examples of catalysts for the dimerization, soluble in hydrocarbons include complexes in which a metal, preferably Nickel, is associated with at least one hydrocarbon group, for example, bis-Nickel, Nickel halide or bis-cyclooctadiene Nickel associated with a halogenated compound of aluminum. Other types of catalysts include complexes formed by mixing at least one compound of Nickel with at least one connection alkylamine and optionally a ligand such as phosphine. These catalysts are well known in the prior art. Examples of catalysts that may be used in such processes are given in Patan what I homogeneous catalysts, which includes a combination of carboxylate Nickel or Nickel chelate with alkylhalogenide or alkylalkoxy respectively. The molar ratio of Al/Ni is from 1.0 to 20.0.

The connection includes Nickel carboxylate, Nickel or Nickel chelate. The Nickel carboxylate, can be represented by the formula (RCOO)2Ni, where R is a branched or unbranched hydrocarbon radical, such as alkyl, cycloalkyl, alkenyl, aryl, aralkyl or Uralkali radical containing at least 2 carbon atoms, preferably the number of carbon atoms, sufficient to make it compatible with the hydrocarbon medium such as a hydrocarbon radical with 5 to 20 carbon atoms, where the radicals can be substituted, for example, hydroxy-group. One of the RCOO-groups, divalent Nickel carboxylate, mentioned above, may optionally be substituted by a group represented by the formula, R1COO-, where R1is halogenosilanes radical containing from 1 to 3 carbon atoms, as described in U.S. patent 4366087.

Examples of Nickel carboxylates include, but are not limited to, bis(2-ethylhexanoate)Nickel; trichloro (or Cryptor) acetate 2-ethylhexanoate, Nickel; about-harbe the spruce 2-ethyl butyrate trichloracetate, Nickel 3,3-dimethylbutyryl triptorelin, Nickel 3,3-dimethylbutyryl trichloracetate, Nickel 4-methylvalerate triptorelin, Nickel heptanoate triptorelin, Nickel heptanoate tribromoacetic, Nickel heptanoate triacetate, Nickel 2-ethylhexanoate monitorizata, Nickel 2-ethylhexanoate trichloracetate, Nickel 2-ethylhexanoate dichloracetate, Nickel 2-ethylhexanoate monochloracetate, Nickel 2-ethylhexanoate tribromoacetic, Nickel 2-ethylhexanoate triacetate, Nickel octoate triptorelin, Nickel octoate trichloracetate, Nickel decanoate triptorelin, Nickel decanoate trichloracetate, Nickel monistat triptorelin, Nickel palmitate triptorelin, Nickel dodecylbenzyl triptorelin, Nickel, diisopropylsalicylic trichloracetate, Nickel monistat pentafluoropropionate and Nickel 2-ethylhexanoate heptafluorobutyrate.

Chelate compounds of Nickel, which interact with alkylalkoxysilane described in U.S. patent 3424815 and 4959491. Chelates of Nickel include compounds having the formula

< / BR>
where R and R' independently are hydrogen, alkyl or aryl having up to 10 carbon atoms, or haloalkyl or calidarium having up to 10 carbon atoms, provided that two R' groups are each chelating ligand umeoa aromatic ring, with up to 4 substituents selected from a halogen. Halogenated chelating ligand preferably has up to 15 carbon atoms and from 2 to 8 substituents selected from halogen, but more preferably has up to 10 carbon atoms and from 3 to 6 substituents selected from halogen. Selected from halogen substituents chelating ligand are fluorine, chlorine bromine or iodine, where R' groups together form a divalent radical, in which monotonia configuration is saved as part of the aromatic ring.

The connection of aluminum includes a hydrocarbon alumaguard or a hydrocarbon Olomoucky. Hydrocarbon group typically includes 0, 1 or 2 hydrocarbon groups, and each has from 1 to 20 carbon atoms, usually from 1 to 12 carbon atoms, and the hydrocarbon groups include alkyl, aryl, aralkyl, alkaryl and cycloalkyl. The halogen compounds include from 1 to 6 halides, such as fluoride, iodide, chloride or bromide, preferably which are easily available, such as chloride. Examples of hydrocarbon Alamogordo include AlCl3, ethylaluminum dichloride, ethylaluminum sesquichloride, dichlorethylene, dichlorobutadiene, chloroethylamine or mixtures thereof.

Suitable is lnyh groups, attached to the aluminum.

Optionally, the catalyst may also include a small amount of water, which affects the speed improvement catalytic dimerization. Usually, the amount of water used is sufficient to increase the rate of catalytic dimerization.

At the exit of the reactor, the catalyst can be deactivated in the usual manner, for example with ammonia, and/or an aqueous solution of sodium hydroxide, and/or an aqueous solution of sulfuric acid, or a mixture of organic acid/bicarbonate. Neprevyshenie olefins and alkanes, if present, is separated from the oligomers by distillation or by using any other suitable techniques, such as extraction and the like. Unreacted raw materials can be recycled back into the original thread.

Extensive skeletal-samaritane or diarizonae olefins next turn in alcohols and any of the widely represented surfactants, including nonionic, anionic, cationic and amphoteric surfactants. Branched olefins serve as intermediates for surfactants. Especially branched olefin is Inanna to the olefin during the process of transformation, serves as hydrophila. No specific surfactant or the methods used for the conversion of branched olefins in alcohol or surfactant, are not considered critical to the present invention provided that they do not reconstruct the skeletal structure of the olefin to such an extent that the by-products are not biodegradable or decreases the degree of branching of less than 0.7.

The conversion of branched olefins in the mixture of primary alcohols is usually carried out, for example, hydroformylation, oxidation and hydrolysis, sulfation and hydrogenation, epoxydecane and hydrogenation or the like. When hydroformylating skeletal-samaritane olefins into alkanols interaction with carbon monoxide and hydrogen according to the method of oxosynthesis. The most widely used is a modified method of oxosynthesis using cobalt or rhodium catalyst modified with phosphine ligand, phosphite, arsina cars or pyridine, as described in U.S. patents 3231621; 3239566; 3239569; 3239570; 3239571; 3420898; 3440291; 3448158; 3448157; 3496203 and 3496204; 3501515 and 3,527818. The method is also described in Kirk Othmer, "Encyclopedia of Chemical Technology" nie is a term used in the art to refer to the interaction of the olefin with CO and H2obtaining aldehyde/alcohol, which has one carbon atom more than the original olefin. Often in the art, the term hydroformylation used to refer to the aldehyde, and recovering to alcohol in General, i.e. hydroformylation relates to the production of alcohols from olefins via carbonylation and recovery of the aldehyde. In this case, hydroformylation means the final receipt of spirits.

Examples of catalysts include cobalt hydrocarbon catalyst, the catalyst is a cobalt-phosphine ligand, and the catalyst is a rhodium-phosphine ligand. The choice of catalysts defines a different reaction conditions. These conditions can vary widely depending on the particular catalyst. For example, the temperature may vary from about room temperature to 300oC. When using the catalyst of the cobalt carbonyl, which is also commonly used, temperature range from 150oWith up to 250oC. Any person skilled in the art based on the above links, or any well-known literary istochnikovyedyeniya demonizovana olefins.

The usual reaction conditions, however, are moderate. Recommended temperature in the range from 125oWith up to 200oC. Typically, the pressure is from 2170 to 10440 kPa, but can be chosen at a lower or higher pressure. The ratio of catalyst and olefin is from 1:1000 to 1:1. The ratio of hydrogen and carbon monoxide are a wide range, but usually the ratio is 1 to 10, preferably about 2 moles of hydrogen to one pray carbon monoxide, which is favourable for the resulting alcohol.

The process of hydroformylation can be carried out in the presence of an inert solvent, although this is not necessary. Can be used in a variety of solvents, such as ketones, for example acetone, methylethyl ketone, methylisobutyl ketone, acetophenone and cyclohexanone; aromatic compounds such as benzene, toluene and xylene; halogenated aromatic compounds such as chlorobenzene and orthodichlorobenzene; halogenated paraffin hydrocarbons, such as methylene chloride and carbon tetrachloride; paraffins such as hexane, heptane, methylcyclohexane and isooctane and NITRILES, such as benzonitrile and acetonitrile.

As for the ligand catalyst, ketelbey ether phosphine, diability phosphine, thrillometer (or hexyl) phosphine, diphenylmethylphosphine, diphenylmethylphosphine, triethoxypropane, butyldiethanolamine, triphenylphosphine, dimethylphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, tricholoroethane and appropriate arsine and STIBINE. Bidentate ligands are tetramethyldisiloxane, tetramethylcyclopropane, tetraethylpyrophosphate, tetrabutylphosphonium, dimethylmethylphosphonate, tetraphenylphosphonium, tetraferriphlogopite, tetrafenilporfinato, tetraphenylphosphonium, dimethylmethylphosphonate, diethyldithiophosphate and tetrachlorinated.

Examples of other suitable ligands include phosphabicyclononanes, such as 9-hydrocarbon-9-phosphabicyclononanes, in which the smallest P-containing ring contains at least 5 carbon atoms. Some examples include 9-aryl-9-phosphabicyclo[4.2.1] nonan, (di)alkyl-9-aryl-9-phosphabicyclo[4.2.1] nonan, 9-alkyl-9-phosphabicyclo[4.2.1]nonan, 9-cycloalkyl-9-phosphabicyclo-[4.2.1]nonan, 9-cycloalkenyl-9-phosphabicyclo[4.2.1]nonan and [3.3.1] and [3.2.1] contrasty and their tranvia contrasty.

A mixture of branched primary Speer is in, preferably the last two, more preferably anionic. Specifically, the mixture of branched primary alcohols of this invention can be used as a precursor to obtain anionic sulfates, including alcohol sulfates, and sulfates oxyalkylene alcohol, and nonionic oxyalkylene spirits.

Can be used with any methodology used for the sulfation of alcohols. The mixture of primary alcohols can be directly sulfotyrosine, or first oxyalkylene and subsequent sulfation. A preferred class of the mixture includes at least one anionic surfactant containing a condensation product of a mixture WITH8-C36especially C11-C19branched primary alcohols with (or without) with ethylene oxide and/or propylene oxide, in which the number of taksigrup is in the range from 3 to 12, and the ratio of ethoxy/propoxy ranges from 4 to 12, followed by sulfation.

The main class of anionic surfactants or ethoxysulfuron alcohol can be characterized by the chemical formula:

R'-O-(CH2-CH2-O)x-SO3M (II)

where R' is a branched olefin, hidrovo M is a cation, selected from alkali metal ion, ammonium ion and mixtures thereof. Of course, the surfactant may be oxyalkylated any compounds containing ethylene oxide, except in a mixture or sequentially with ethylene oxide.

Methods of sulfation is described, for example, in U.S. patents 3462525 on August 19, 1969 Levinsky et al., 3428654 on February 18, 1969 Developing et al., 3420875 from 7 January 1969 DiSalvo et al., 3506580 dated April 14, 1970 Developing et al., 3579537 may 18, 1971 Developing et al. and 3524864 dated August 18, 1970 Developing et al. Suitable methods of sulfation include sulfation with sulfur trioxide (SO3), sulfation chlorosulfonic acid (lSO3N) and the sulfation of sulfamic acid (NH2SO3N). When using concentrated sulfuric acid to produce sulfates of alcohols concentrated sulfuric acid is typically an acid with a concentration of from 75 to 100, preferably from 85 to 98 wt.% in the water. A suitable amount of sulfuric acid are usually from 0.3 to 1.3, preferably from 0.4 to 1.0 mol of sulfuric acid per mole of alcohol.

The usual method of sulfation with sulfur trioxide involves the interaction of liquid alcohol or its ethoxylate and gaseous sulfur trioxide at a pressure which ranges from 25oWith up to 70oWith the receipt of ester of sulfuric acid of a given alcohol or its ethoxylate. Ester of sulfuric acid alcohol or its ethoxylate then released from the column with a flowing film and neutralized with a solution of an alkali metal, for example sodium hydroxide or potassium hydroxide, to obtain the salt of sulfate of alcohol or salt ethoxysulfuron alcohol.

Suitable oxyalkylene alcohols can be obtained by adding to oxyalkylation alcohol or mixture of alcohols of the calculated amount, for example from 0.1 to 0.6, preferably from 0.1 to 0.4 wt.% in relation to the total number of alcohol, of a strong base, typically an alkali metal hydroxide or alkaline-earth metal, such as sodium hydroxide or potassium hydroxide, which serve as a catalyst for oxyalkylene. The resulting mixture is dried, removing any water present in the form of steam, then enter the amount of oxide alkylene calculated to obtain from about 1 mole to about 12 moles of oxide alkylene per mole of alcohol and the resulting mixture is allowed to interact until used all the oxide alkylene, over the course of the reaction being followed by reduction of the reaction pressure.

Oxyalkylene usually carried out at>C, preferably from 140oWith up to 160oC. Suitable reaction pressure is achieved by introducing into the reaction vessel the required amount of oxide alkylene, which has a high vapor pressure at the desired reaction temperature. From the point of view of the security process, the partial pressure of the reactant oxide alkylene preferably limited, for example, to less than 512 kPa, and/or the reagent is preferably diluted with an inert gas, such as nitrogen, for example, the concentration in the vapor phase is about 50% or less. The reaction, however, can safely be carried out at higher concentrations oxide alkylene greater than the total pressure and the greater the partial pressure of the oxide alkylene, if the relevant precautions are known in the art, to control the risk of explosion. As for ethylene oxide, particularly preferably the total pressure from 376 to 858 kPa and the partial pressure of ethylene oxide from 345 to 621 kPa, more preferred are the total pressure from 3,515 kg/cm2(50 psi) to 6,328 kg/cm2(90 psi) and the partial pressure of ethylene oxide from 238 to 445 kPa. Pressure is a measure to determine the extent of reaction and the reaction is almost completed, if having to introduce a desired average number of units monoxide alkylene per mole of oxyalkylated alcohol. For example, treatment of a mixture of alcohols with 3 moles of ethylene oxide per mole of alcohol serves to amoxilonline each molecule of alcohol an average of 3 units of ethylene oxide per mole of alcohol, although a significant part of the alcohol components are connected with more than 3 parts of ethylene oxide and approximately equal to the part must be connected to less than 3. In a typical mixture of the product of amoxilonline there is a small part of the unreacted alcohol.

Other oxide alkylene can be used, such as propylene oxide and butylenes. They can be added in the form of a heterogeneous mixture of the alcohol or sequentially to obtain a structure in the form of a block.

A mixture of sulfonated primary alcohols of this invention can be used as surface-active substances with a wide range of applications, including detergents, such as granulated detergent powders, liquid, means for washing liquid for washing dishes; and in a variety of compositions, such as detergent wide use, liquid Soaps, shampoos and liquid detergents.

A mixture of sulfonated primary alcohols of this invention particularly finds application art sulfated primary alcohols of this invention:

other surfactants of ionic, nonionic, amphoteric or cationic type,

modifying additives (phosphates, zeolites), somodevilla additives (polycarboxylate),

bleaching agents and activators,

the agents controlling the pricing,

enzymes

agents that prevent the appearance of a gray shade in linen,

optical Brightener and

the stabilizers.

Liquid funds for washing clothes usually include the same components as the granulated detergent powders, but usually contain less inorganic modifiers. In liquid media for washing clothes often contain hydrotropic. Cleaning products for wide applications typically include other surfactants, builders, agents, controlling foaming, hydrotropes and solubilizing alcohols.

In addition to surface-active agents, detergents and cleaning agents can contain a large number of salts of reactive substances in quantities of up to 90 wt.% weight, preferably from 5 to 35 wt.%, to enhance the cleaning action. Examples of conventional non-organic modifying agents include phosphates, polyphosphates,carboxylate, aminocarboxylate, such as ethylenediaminetetraacetate, nitrilotriacetate, hydroxycarboxylic, citrates, succinate and substituted and unsubstituted, alkindi - and polycarboxylic acids. Another type of modifying additives used in the granular washing powders and liquid means for washing clothes are different, essentially water-insoluble materials which are able to reduce the hardness of water, for example, by the ion exchange process. In particular, for this purpose, a very useful set of silicates of sodium, known as zeolites of type A.

The composition may also contain peroxide compound with bleaching effect, such as perborate, percarbonate, persulfates and organic peroxyacids. Compositions containing peroxide compounds may also contain stabilizing agents, such as magnesium silicate, sodium ethylenediaminetetraacetate or sodium salt of phosphonic acids. In addition, to improve the efficiency of inorganic persona at low temperatures can be used bleaching activators. Especially used for these purposes are substituted amides of carboxylic acids, for example, tetraacetylethylenediamine, substituted CT is rotronic substances include alkali metal salts of sulfonic acids of benzene, toluene and xylene; alkali metal salts of formic acid, citric acid and succinic acid, chlorides of alkali metals, urea, mono-, di - and triethanolamine. Examples solubilizers alcohols include ethanol, isopropanol, mono - or polyethylene glycols, monopropellant and ethers alcohols.

Examples of agents that control the foaming, include soap-based fatty acids with high molecular weight, paraffinic hydrocarbons and defoamers containing silicone. In particular, hydrophobic silica particles are effective agents controlling foaming in such compositions for washing clothes.

Examples of known enzymes that are effective when used in vehicles for washing clothes, include protease, amylase and lipase. Preference is given to those enzymes that have optimal efficiency in created conditions for detergent and cleaning agent.

The literature describes a large number of fluorescent brighteners. For compositions that are intended for washing clothes, especially suitable are derivatives diaminostilbene and substituted distribiter.

As agents, predator is second nature. Examples include water-soluble polyanionic polymers, such as polymers and copolymers of acrylic and maleic acids, derivatives of cellulose, such as carboxymethyl cellulose, methyl - and hydroxyethylcellulose.

In addition to one or more of the above other surface-active compounds and other components of the detergent compositions of this invention typically contain one or more inert components. For example, the balance of the liquid detergent compositions typically in an inert solvent or diluent, usually water. Powder or granular compositions usually contain some inert fillers or carriers.

The following examples illustrate the invention.

Example 1

This example shows getting a skeletal-isomerizing C16the olefin consistently turn in a mixture of skeletal-isomerized C17primary alcohols of the present invention.

1 liter of NEODENE 16 olefin, C16linear-olefin, commercially available from Shell Chemical Company first dried and purified through a layer of aluminum oxide. Then the olefin is passed through a tube furnace at a temperature of approximately 250oWith scroot. Starting from the top, a tubular furnace loaded with glass wool, and then 10 ml of silicon carbide, then the catalyst and then 5 ml of silicon carbide, and additionally glass wool at the bottom. The volume of the tube furnace is 66 ml. Reactor tube furnace has three temperature zones, with a thermocouple having a large scale, is inserted in a tubular reactor and located so as to control the temperature of the top, bottom, and at three different points catalytic layer. The reactor is turned and mounted in the furnace. In all three zones, including the zone of the catalyst during reaction, keep the temperature around 250oC and the pressure in the reactor is maintained at level 114 kPa.

The amount used of the catalyst is 23.1 g, or 53 ml volume. The type of catalyst used for structural isomerization NEODENE 16 olefin is a 1,59 mm extruded and calcined H-ferrierite containing 110 hours/million palladium.

This catalyst was prepared according to the example of U.S. patent 5510306, partially reproduced in this description for convenience. Ammonium-ferrierite having a molar ratio of silicon dioxide and aluminum oxide 62:1, the surface area of 369 m2on g (R/Ro=0,0 underwater zeolite. The components of the catalyst are converted into a paste using the Lancaster mix muller. Pasty material catalyst ekstragiruyut using 25.4 mm or 57,2 mm Bonnot extruder, pin barrel.

The catalyst is prepared using 1 wt.% acetic acid and 1 wt.% citric acid. In Lancaster mix muller download 645 g ammonium-ferrierite (5,4% loss on ignition) and 91 grams of CATAPAL alumina (D (PNP 25,7%). Aluminum oxide is mixed with ferrierite for 5 minutes, then add 152 ml of deionized water. For peptization of the alumina in pasteurisation slowly add a mixture of 6.8 g of glacial acetic acid, 7.0 g of citric acid and 152 ml of deionized water. The mixture turns into a paste for 10 minutes. Then slowly add 0.20 g of tetranitro palladium 153 g of deionized water while the mixture is ground for 5 minutes. Add 10 g of METHOCEL F4M hydroxypropylmethylcellulose and the mixture of zeolite/alumina milled for a further 15 minutes. Extrusion mixture has a DUP of 43.5%. The mixture of zeolite/alumina of 90:10 is transferred into 57,15 mm with 2.25-inch Bonnot extruder and ekstragiruyut using a matrix with holes 1,59 mm

Raw extrudate is dried on the shelves in the oven, heated to a temperature of 150oFrom within layaout. The extrudate calicivirus in the air stream at a temperature of 500oC for 2 hours.

Olefin is passed through the reactor furnace for more than 5 hours. Samples 36,99 g and 185,38 g are selected in a time of 1 hour and 5 hours and unite with obtaining the total weight of 222 g of this sample is then distil under vacuum at a pressure of 0.533 kPa obtaining a predominant amount of C16skeletal-isomerizing of olefin, collecting fractions of distillate, boiling at a temperature of 160oWith the cube and at a temperature of 85oWith the above and at a temperature of 182oWith the cube and at a temperature of 75oWith the above.

A sample of 90 g 110,93 g skeletal-isomerizing the olefin then hydroformylation using a modified oxazines. 90 g of skeletal-isomerizing of olefin is subjected to interaction with hydrogen and carbon monoxide at a molar ratio of about 1.7:1 in the presence of cobalt catalyst modified phosphine at a temperature up to about 185oC and a pressure of about 7684 kPa for 4.5 hours at 300 cm3the autoclave purged with nitrogen. After completion of the reaction product is cooled to a temperature of 60oC.

40 g hydroformylating product poured into 100 ml flasks is to end 165oC. Fractions of distillate 20,14 g and 4.12 g collected at a temperature of 155oWith 165oS, respectively, and combined in a 100 ml flask.

The fractions of the distillate flask add 0.2 g of sodium borohydride, stirred and heated to a temperature of 90oWith over 8 hours to deaktivirovana catalyst hydroformylation and stabilization of alcohols. Distilled alcohol is washed with water at a temperature of 90oWith three times, dried over sodium sulfate and filtered into a 100 ml flask. The alcohol is then subjected to vacuum distillation for another 4 hours to drive off the remaining

water. The product is then subjected to NMR analysis and sulfation to test its solubility in cold water, the washing ability and biological degradability.

Example 2

This example shows getting a skeletal-isomerizing C13-14the olefin, then turn the mixture skeletal-isomerized C14-15primary alcohols of the present invention.

C13-14linear internal olefin having the structure of 53,38% linear C13the olefin, 45,24% linear C14the olefin, 0,96% branched C13the olefin and 0,29% branched C14the olefin, put through a tubular furnace for 26 h, except that after 8 hours the temperature of the furnace increases in all three zones up to 275oC. At the point in time is 13 hours, 18 hours, 20 hours and 26 hours, selected samples of skeletal-isomerized olefins and unite with obtaining the total weight of 774

Samples of the gaseous and liquid products, selected after 4.5 hours (at a temperature of 250oC) and 15.5 hours (at a temperature of 275o(C) in the flow analyze to determine their composition. At a temperature of 250oWith turns 70.1% of C13olefinic feedstock and 75.6% C14olefinic feedstock. At such levels of transforming the selectivity to branched C13and C14the olefins is 96,3% and 97.8%, respectively. 67,4%14alafinova raw materials emit in the form of a skeleton-isomerizing 13branched olefin. 74,0% C14olefinic raw materials emit in the form of a skeleton-isomerizing branched C14the olefin.

At a temperature of 275oWith, becomes 79,4% C13olefinic feedstock and 82.2% WITH14olefinic feedstock. At such levels of transforming the selectivity to branched C13and C14the olefins is of 91.5% and 92.1%, respectively. 72,6% C13aleinov Ira isolated in the form of a skeleton-isomerizing branched C14the olefin.

Skeletal-isomerized olefin is then subjected to vacuum distillation at a pressure of 0.533 kPa. Collect 636 g of distillate boiling in the cube at a temperature in the range of from 135oWith up to 145oWith the above in the range from 108oWith up to 138oC.

606 g of skeletal-isomerizing of distilled olefin hydroformylation according to the above method, except that the process is carried out in there are 3,785 l autoclave, using a molar ratio of odnokile carbon and hydrogen 37/63 mol.% for 12-13 hours at a pressure of from 4826 to 5516 kPa and a temperature of 175oC. Collect 693 g of alcohol.

The alcohol is then subjected to flash distillation at a pressure of 0.533 kPa with getting C14-15alcohol, collecting approximately 650 grams of distillate boiling in the cube at a temperature of 185oWith the above at a temperature of 140oC. This fraction is treated with 5.0 g sodium borohydride, is heated to a temperature of about 100oC and then treated for another 5.0 g sodium borohydride in the total time of heating 9 hours. The alcohol washed with water at a temperature of 90oWith three times, dried over sodium sulfate, filtered and subjected to vacuum distillation at a pressure of 0.533 kPa. Fraction of distillate, boiling at a temperature of from 128

Example 3

The procedure described in example 1 is used for the skeletal isomerization of NEODENE 14 olefin, commercially available from Shell Chemical Company, which is C14-olefin, with subsequent transformation into a mixture of skeletal-isomerized WITH15primary alcohols. Tube furnace maintained at a temperature of 250oC. Collect skeletal isomerized distillate, boiling at a temperature of 133oWith the cube and at a temperature of 64oWith the above and hydroformylation when the pressure 8963-9653 kPa for 5 hours at a molar ratio of H2/CO 1,7: 1, using the equipment described in example 1.

Example 4

The procedure described in example 1 is used for the skeletal isomerization of NEODENE 12 olefin, which is C12-olefin, with subsequent transformation into a mixture of skeletal-isomerized C13primary alcohols. Skeletal-isomerized olefin is subjected to vacuum distillation at a pressure of 2,665 kPa, collecting the distillate, boiling at a temperature of 172oWith the cube and at a temperature of 105oC at the top and hydroformylation with obtaining alcohol. Use equipment used in example 2, when the pressure 2032 kPa in Technika, collect the fraction boiling at 141-152oWith the cube and 127-132oWith the above.

Example 5

Repeat the operation using the type of the olefin, the method and equipment that were used in example 2. WITH13-14internal olefin skeletal-isomerized at a temperature of 250oC. Isomerized olefin is subjected to vacuum distillation at a pressure of 0.533 kPa obtaining fractions of distillate, boiling at 95oWith 77oWith the above, as well as receive when pressure 2,665 kPa fractions of distillate, boiling at a temperature of from 120oWith up to 175oWith the cube and from 73oWith up to 106oWith the above. Hydroformylation carried out in the autoclave for about 9 hours at a pressure 8032 kPa, using the ratio of the gases CO and N 37/63 mol. %. Next, collect the fraction of distillate, boiling at 173oWith the cube and 125oFrom upstairs, and treat it with sodium borohydride as in example 2.

Example 6

Each of the mixtures of primary alcohols described in examples 1-6, sulfation, adding dropwise chlorosulfonic acid to a mixture of primary alcohols. Specifically, a mixture of primary alcohols blow in 2-3 hours with nitrogen in the flask, then add about 1 ml of methylene chloride per gram of the mixture of primary alcohols. Chlorsulfuron about 30-35oC. If the solution becomes viscous, add methylene chloride. Then the solution is rinsed with nitrogen for 2-3 minutes to remove the HCl, after which it is added slowly to a chilled 50% sodium hydroxide in 3A alcohol solution to neutralize the mixture of primary alcohols. If the pH is lower than 8, add more alkaline solution up until the pH is 8-9. If the solution is too alkaline, add 50% solution of H2SO4to bring the pH. The solution is stirred for another hour and the pH is adjusted accordingly to the specified level. The methylene chloride is removed on a rotary evaporator under reduced pressure at a temperature of approximately 40oWith injecting nitrogen.

The mixture of primary alcohols further testing to determine the number, type and location of the side chains using the methodology developed by JMSE NMR, as described above. For the determination of Quaternary carbon atoms using the method quat only JMSE NMR, as described above. The results of this test are presented in table I. Samples of sulfated primary alcohol testing on biological degradability, the results of these tests are presented in table II; the washing ability, the results are presented in table III. The examples included in tablular product of the corresponding example. Each of these tests are conducted according to the procedures described above. As a comparative example using NEODOL 45-sulfate, which is tested to determine branching, biological decomposing and detergency. NEODOL 45-S was used as a comparative example, as it is currently available commercial mixture of primary alcohols, which after sulfation, typically used in detergents and is known as the easily biodegradable.

The above results show that skeletal-samaritane branched alcohols of the present invention have a very high average number of side chains in chain molecules, much superior to 0.7, while commercial NEODOL 45 is the average number of side chains, which is significantly lower order of 0.3. The types of side chains are strikingly similar for the different alcohols of the present invention except that the branched C17there is no branching at leaf carbon (limit isopropyl). The results also show a sharp increase in the number of side chains, available at3in comparison with the absence of any side chains of NEODOL 45 alcohol in position * skeletal-isomerized alcohols, and NEODOL alcohol. However, the methyl side chains of skeletal-isomerized alcohols are not concentrated in the position of C2as NEODOL 45 and other common alcohols related to certain detergents. Another feature of the skeletal-isomerized alcohols is that they contain a larger number of side chains ethyl type than NEODOL 45. Further, except for the C17branched alcohol, most of them also skeletal-samaritano on terminal parts of hydrophobe that shows a high percentage of the formed end isopropyl, by contrast with NEODOL 45, where they were not found.

The results also confirm the conclusion that the predominant number of the side chains in skeletal-isomerized alcohols are more concentrated towards the ends of the chain molecules, i.e. WITH2WITH3and isopropyl limit positions than towards the center of the chain molecules. The NMR data show a high percentage of methyl, ethyl and ISO-propyl side chains of compounds, side chains which are predominantly located towards the centre of the chain, that is directed inward from the fourth carbon atom from either end of the chain, usually with a low percentage Boko is tons of methyl, ethyl and ISO-propyl types of side chains, and a significant number of side chains, available in2and C3positions, indicating that the molecule has a greater concentration of the side chains in the C2and C3the provisions of the carbon at the ends of the carbon chain than the number of side chains, available in4or more distant positions from both ends of the molecule, located inside towards the center.

Finally, despite the significant number of side chains on the chain molecules, the Quaternary carbon atoms, determined by a modified method of NMR JMSE, were not found. These data suggest that these compounds will be easy to decompose biologically.

OECD 301D results of biological decomposition show that each of the sulphate mixtures of primary alcohols of this invention are easily biodegradable. Some of sulfated mixtures of primary alcohols of this invention even show 100% biodegradation in 28 days.

LSD95(least significant difference at 95% probability) is equal to 5.0 at both temperatures.

The test results on ability to show that a mixture of su is, for example, 6-2 is far superior to the sulfated NEODOL alcohol in detergency as in cold and warm water, although they have the same chain length. A composition having good ability in cold water is that which is superior, in relation to alcohol NEODOL with the same chain length, the washing ability in cold water. Preferred, however, are the sulfates of alcohols, which have the ability in cold water 22% or higher, most preferably 28% or higher.

Example 7

This example shows getting dimenisonal monorities C12-C15alcohol from internal olefins using halachically catalyst.

Flask is charged with 2268,7 g of a mixture WITH6-C8internal olefins containing some4WITH5WITH9WITH10olefins, and distil using Oldershaw distillation columns with 11 plates, equipped with multi reflux condenser with an offset cylinder, cooled with dry ice, and containing a layer of nitrogen. After 37 hours of distillation fractions, Athanasius at temperatures up to 138oWith the cube and 125oWith the top of the column, collect from obtaining a total number of 1200, These fractions presti technique. 1200 g of the olefin poured into a 5-liter round bottom flask equipped with a condenser, a condenser with dry ice, a thermocouple, a water bath containing a layer of nitrogen. Successively added to 19.74 g of dry hexafluoroacetylacetonate Nickel (Nickel catalyst) and 53,76 g 11/89 wt.% solution diethylaluminium ethoxide in cyclohexane (solution of aluminum) and is mixed with the olefin. The reaction mixture is heated to a temperature of 35oC for 6.5 hours, then add another 14,38 g of a solution of aluminum heated to a temperature of 37oC for another 2 hours, then add 4.0 g of Nickel catalyst and of 13.75 g of a solution of aluminum is heated to a temperature between 35oWith up to 37oC for 10 hours, then add another 15,55 g of a solution of aluminum followed by heating for another 4 hours, then add another 4 g of Nickel catalyst and 14.4 g of a solution of aluminum followed by heating for another 5 hours, then add another to 21.0 g of a solution of aluminum and 5.0 g of Nickel catalyst, followed by heating for another 3 hours, then add another 4,18 g of Nickel catalyst and 20.1 g of a solution of aluminium.

Next, the reaction product in the flask was quenched with 100 g of citric key is 4-8
olefin is subjected to further distillation to obtain fractions containing predominantly C13-14olefins. The distillation is carried out as above, except that use 10-disc column Oddershaw, and collecting the fraction which distills at a temperature of from 169oWith up to 194oWith the cube and from 129oWith up to 155oWith the top of the column, the vacuum 6,3-6,4 kPa, the total number 188,05,

150 g of this boot then subjected to hydroformylation 500 ml autoclave, using a modified oxazines. 150 g dimenisonal of olefin is subjected to interaction with carbon monoxide at a ratio of N2/CO = 2, in the presence of cobalt catalyst modified with phosphine and potassium hydroxide in ethanol at temperatures up to 180oWith, the stirring speed of 1250 rpm and the pressure 6894 kPa for 20 hours. After completion of the reaction product is cooled to a temperature of 60oC.

Hydroformylation diarizonae alcohols undergo further flash evaporation to separate any unreacted olefins and paraffins. Collect fractions, Athanasius at a temperature of from 182oWith up to 250oWith the cube and from 99oWith up to 112oWith the above, and natraul and heated to a temperature of 50oWith add 0.6 g sodium borohydride and subject interaction for 2 hours, then add another 0.6 g of sodium borohydride and left to interact for further 1.5 hours at a temperature of 75-80oWith and then left to interact for further 2.5 hours at a temperature of 98-100oC. the Solution is cooled, transferred to a 500 ml flask, washed by shaking with deionized water at a temperature of 70oWith vented, stand, add 20 ml of ethyl ether, shaken and separated. The aqueous phase is drained off and the process repeated two more times using ethyl ether. After washing the alcohol, add 10 g of sodium sulfate, shake and then stand. The product is filtered, the liquid is transferred into a 250 ml flask and then subjected to further distillation to remove from the solution of light fractions. The distillate obtained at temperatures of up to 102oWith the cube and 163oFrom the top, drop and 82,91 ml residue in Cuba emit. This balance includes mooretwin C12-16alcohols, with 42% WITH1444% OF THE C15and 8%, C16alcohols, according to GHS, and it is subjected to analytical testing and further reactions to obtain sulfates.

Example 8

This example demonstrates receive the left catalytic Converter.

Use the same technique as in example 1 above, with the following exceptions. The amount of distilled4-10olefin is 2427,7, Collect 712,5 g of distillate, boiling at a temperature of from 120oWith up to 154oWith the cube and from 89oWith up to 129oWith the above. A reflux set to activate for 5 seconds and off for 7 seconds. Fractions of distillate are mainly internal olefins with carbon chain WITH6-9. 702,6 g these olefins will timeresult a 2-liter flask, using 0,493 g 2-ethylhexanoate-trifenatate Nickel in 5 ml of cyclohexane and 12 ml of 1 molar solution ethylaluminum dichloride in hexane (first catalyst loading) as catalysts for the dimerization, can be injected into the olefin. The contents of the flask are heated to a temperature of 35-38oWith the average during the entire reaction. After about 3 hours of heating add a second catalyst loading in the same amount. After one hour heating type third catalyst loading in the same amount and after a further 1 hour 15 minutes add the fourth catalyst loading in the same amount. After 6.5 h add a fifth catalyst loading in the same amount and even after 7 hours of heating add it is utilizator in the same amount. The contents of the flask heated for another hour.

To neutralize the catalyst for the dimerization of 22 g of sodium bicarbonate in 250 g of deionized water is added to 100 g of citric acid in 100 g of deionized water, to which add more water to produce 1 litre boot. Diarizonae olefins pour in a 2-liter separating funnel in 1/2 l of a solution of citric acid/sodium bicarbonate, shake and blow, share and repeat the operation. Neutralized dimenisonal solution is dried over sodium sulfate as described above.

As in example 1, olefins next distil with obtaining6-9olefins. Collect fractions of distillate, boiling at a temperature of 157oWith the cube and 125oWith above under the pressure 5.5 kPa, and boiling at a temperature of from 139oWith up to 164oWith the cube when the pressure 1,866 kPa boiling at a temperature of from 179oWith up to 240oWith the cube at a pressure of 1.9 kPa total number 231,95 g of distillate.

Dimenisonal distillate hydroformylation as described above and flash distil at a pressure of about 0.5-0.7 kPa. Add 1.39 g sodium borohydride to 211,48 g distilled alcohol, heated to a temperature of 50oC for 1 hour, then add eoct washed as described above and re-distil with obtaining fractions of the distillate, boiling at a temperature of from 141,5oWith up to 240oWith the cube and from the 100oWith up to 104oWith the above under a pressure of 0.4 kPa. Mooretwin C13-17alcohols having 25% C14, 40% C15and 25% of C16alcohols, according to GHM, harvested and subjected to analytical testing and sulfation as described below.

Example 9

This example shows getting a C13,15,17demonizovana mooretwin alcohols from alpha-olefins.

In this example, a mixture of 600 g of NEODENE 6-olefin, WITH6the olefin and 800 g of NEODENE 8-olefin, WITH8the olefin containing 5.32 g ethylaluminum dichloride add in a 5-liter flask. Using the method of example 1, with the following differences. Add a solution of 7.9 g of 2-ethylhexanoate-trifenatate Nickel 6.35 g of cyclohexane (solution of Nickel) and heated. The temperature of the flask support from the 33oWith up to 38oWith throughout the reaction. Even with 7.6 ml of a solution of aluminum obtained in example 2 and 5 ml of a solution of Nickel injected into the reaction flask after heating for about 8 hours

To neutralize demonizovana olefins using 1.5 l of neutralizing a solution of sodium citrate, share and neutralization repeat. Dimenisonal product distill is SUP>oWith the top at a pressure of 8.0 kPa, Athanasius at a temperature of from 120oWith up to 133oWith the cube and from 110oWith up to 122oWith the top at a pressure of 1.2 kPa and Athanasius at a temperature of from 127oWith up to 149oWith the cube and from 118oWith up to 145oWith the top at a pressure of 1.3 kPa total number 786,4,

730 g of these demonizovana olefins hydroformylation in there are 3,785 l autoclave, conducting the reaction at temperatures up to 240oC and pressures up 7894 kPa.

809 g hydroformylating olefin is treated with 6.5 g sodium borohydride, as described above, and then further adding 6.5 g sodium borohydride and heating, and a third addition of 4.95 g followed by heating for 6 hours to a temperature of 99oC.

Processed hydroformylating olefins washed as described in example 1, filtered and distil with obtaining fractions, Athanasia at a temperature of from 152oWith up to 181oWith the cube and from 173oWith up to 172oWith the top at a pressure of 0.8 kPa total number of 495 g C13C15and C17mooretwin alcohols. Sample analytical testing and sulfation as described below.

Example 10

Each of the mixtures mooretwin alcohols, Opio, through the alcohol mixture in the flask was bubbled within 2-3 h of nitrogen, and then add about 1 ml of methylene chloride per gram of the mixture of alcohols. Chlorosulfonic acid are added dropwise to a mixture of alcohols for about 25 minutes, maintaining the temperature 30-35oC. If the solution becomes viscous, add methylene chloride. Then the solution bubbled nitrogen for 2-3 minutes to remove the HCl, after which it is added slowly to a chilled 50% sodium hydroxide in 3A alcohol solution to neutralize the mixture of alcohols. If the pH is lower than 8, add more alkaline solution, up until the pH becomes 8-9. If the solution is too alkaline, add 50% solution of H2SO4to bring the pH. The solution is stirred for another hour and the pH is adjusted accordingly to the specified level. The methylene chloride is removed on a rotary evaporator under reduced pressure at a temperature of approximately 40oWhen the bubbling of nitrogen.

The mixture of alcohols of examples 7-9 further testing on the number, type and location of the side chains using the methodology developed by JMSE NMR, as described above. For the determination of Quaternary carbon atoms using the method quat only JMSE NMR. The results of this test are presented in table IV. The average number adamowitsch degradability, the results of these tests are presented in table V; washing capacity, the results are presented in table VI. The samples given in the table, arranged in order, according to the length of the chain to facilitate review and identified as 10-mean sulfate relevant example. Each of these tests are conducted according to the procedures described above. As a comparative example presents NEODOL 45-sulfate, which is tested to determine branching, biological decomposing and detergency. NEODOL 45-S was used as a comparative example, as it is currently available commercial mixture of primary alcohols, which when sulfation is typically used in detergents and is known as the easily biodegradable. Also for comparison in testing biological degradability included sulfated alcohol EXXAL-13S, presumably mainly containing C13 alcohols and obtained by oligomerization of propylene using an acid catalyst and then subjected to hydroformylation using oxazines. As indicated in the literature, EXXAL 13 has about 3-4 methyl side chains in the molecule trimetilazetta.

The results of the th side chains according to NMR analysis. Specifically, a very small number of side chains are located in the positions of the carbon C2-4. As the average number of side chains demonizovana alcohols is significantly higher than the NEODOL alcohols, the center of the main carbon chain of the molecule should be there, where the main number of the side chains, i.e., the excess of 80%. Under the center refers to the situation4inward from each end of the molecule.

Also worthy of attention, a higher percentage of ethyl side chains of demonizovana alcohols of this invention in comparison with a relatively small amount of ethyl side chains found in the NEODOL alcohol.

OECD 301 D test results of biological decomposition show that every composition sulfated primary alcohol of the present invention is easily biodegradable, as well as sulfated NEODOL alcohol. Sulfated alcohol EXXAL biodegradable very slightly.

LSD95(least significant difference at 95% probability) is equal to 5.0 at both temperatures.

Evaluation of detergency show that diarizonae alcohols of this invention have superior or the Mixture of branched primary alcohols, having from 11 to 36 carbon atoms with the average number of side chains, including methyl and ethyl side chains, from 0.7 to 3.0 molecule.

2. A mixture of branched primary alcohols under item 1, characterized in that the average number of side chains per molecule ranges from 1.0 to 3.0.

3. A mixture of branched primary alcohols under item 1 or 2, characterized in that the average number of side chains per molecule ranges from 1.5 to 2.3.

4. A mixture of branched primary alcohols according to any one of paragraphs.1-3, characterized in that the molecules of alcohols include less than 0.5 at.% Quaternary carbon atoms.

5. A mixture of branched primary alcohols according to any one of paragraphs.1-4, characterized in that the mixture contains less than 5% of linear alcohols.

6. The mixture according to any one of paragraphs.1-5, characterized in that the alcohols contain at least 40% of the methyl side chains of the total number of side chains.

7. A mixture of branched primary alcohols according to any one of paragraphs.1-6, characterized in that the alcohols contain from 5 to 30% ethyl side chains of the total number of side chains.

8. The method of obtaining a mixture of branched primary alcohols under item 1, including the isomerization of the olefin in the presence of Camisa fact, the method involves the following stages: a) the interaction of the original olefin containing linear olefins having at least 10 carbon atoms with a catalyst effective for skeletal isomerization of the specified linear olefin obtaining branched olefin with the same number of carbon atoms; and (b) convert the specified branched olefin in the mixture of a primary alcohol, and a catalyst for the skeletal isomerization includes a molecular sieve having at least one channel with crystallographically free diameter along the X and/or Y-plane [001] in the range from 0.42 to 0.70 nm, where the molecular sieve is preferably a zeolite having ferrierite-isotype structure, and the conversion of olefin to alcohol at the stage b) is achieved by hydroformylation of the olefin with carbon monoxide and hydrogen, in the presence of a catalyst of hydroformylation.

9. The method of obtaining a mixture of branched primary alcohols under item 1, having from 13 to 21 carbon atoms, comprising the dimerization of the olefin in the presence of a catalyst and the subsequent conversion of the obtained branched olefin in the mixture of branched primary alcohols, characterized in that the method comprises the stage of: (a) dimerize even obtaining12-C20branched olefin; and (b) the transformation is specified WITH the12-C20a branched-chain olefin in the specified mixture of branched primary alcohols, and the specified dimerization catalyst comprises a combination of Nickel carboxylate with alkylhalogenide, or a combination of Nickel chelate with alkylalkoxy; and the conversion of olefin to alcohol at the stage b) is achieved by hydroformylation of the olefin with carbon monoxide and hydrogen, in the presence of a catalyst of hydroformylation.

10. The method according to p. 9, characterized in that the starting olefin comprises at least 90% linear olefins.

11. The method according to p. 9 or 10, characterized in that the starting olefin comprises at least 50% of internal olefins.

12. A mixture of alkoxylated branched primary alcohols obtained by the interaction of a mixture of branched primary alcohols according to any one of paragraphs.1-7 connection with ethylene oxide.

13. A mixture of alkoxylated branched primary alcohols under item 12, characterized in that alkoxylate preferably is an ethoxylate obtained by the interaction of a mixture of branched primary alcohols with ethylene oxide.

14. A mixture of branched primary alkylsulfate the branched alkoxycarbonyl primary alkyl sulphates, received by alkoxysilanes and sulfation mixture of branched primary alcohols according to any one of paragraphs.1-7.

16. Washing composition comprising: a) one or more surfactants selected from the group comprising alkoxylated branched primary alcohols under item 12, branched primary alkyl sulphates on p. 14 and branched alkoxycarbonyl primary alkyl sulphates on p. 15; (b) modifying additive; and (C) optionally one or more additives selected from the group comprising agents that control the foaming, enzymes, bleaching agents, bleach activators, optical brighteners, somodevilla additives, hydrotropes and stabilizers.

17. Washing composition according to p. 16, wherein the modifying additive selected from the group including carbonates, alkali metal silicates, sulphates, polycarboxylate, aminocarboxylate, nitrilotriacetate, hydroxycarboxylic, citrates, succinate, substituted and unsubstituted alkane di - and polycarboxylic acids, complexes of aluminosilicates and mixtures thereof.

18. Washing composition according to p. 16 or 17, characterized in that the bleaching agent, selected from the group including perborate, percarbonates, persulfates, org is water whitening selected from the group comprising amides of carboxylic acids, substituted carboxylic acids, and mixtures thereof.

20. Washing composition according to any one of paragraphs.16-19, characterized in that hydrotap chosen from the group comprising alkali metal salts of aromatic acids or alkylcarboxylic acids, chlorides of alkali metals, urea, mono - or polyalkylene and mixtures thereof.

21. Washing composition according to any one of paragraphs.16-20, characterized in that it is either granulated washing powder or liquid for washing or dishwashing soap, or soap, or shampoo, or detergent.

 

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The invention relates to detergents used in technological processes, in particular in the manufacturing industry, automobile and machinery for cleaning metal surfaces from contamination by oils, emulsions, greases
The invention relates to detergent compositions that can be used by the relevant food industry for cleaning and disinfection of production areas and equipment throughout the process

The invention relates to the cleaning of metal and polymer surfaces, as well as the skin of humans and animals from organic and bacterial contamination, and can be used in machine-building, instrument-making, electronics and electrical engineering, repair and maintenance of all types of transport, utilities, medicine and medical establishments, swimming pools, etc

The invention relates to a paste-like means for washing tableware - metal, glass, porcelain, crystal and simultaneously cleaning of tiles and sanitary wares

The invention relates to liquid detergent and technical disinfectants and can be used in the food industry

Sanitary cleaner // 2195479
The invention relates to cleaning tools designed for effective removal of resistant formations rust, sediment, hardness salts with toilets, porcelain sinks and tile surfaces
Detergent // 2171831
The invention relates to detergents used for industrial cleaning of metallic and non-metallic surfaces from different types of pollution, including from pollution by oil and other liquid hydrocarbons

Cleaner glass // 2167192
The invention relates to household chemicals, in particular to means for cleaning automotive glass
Detergent // 2144946
The invention relates to detergents for cleaning of various contaminants, including petroleum products
The invention relates to the field of purification of sewage from fat and organic deposits and can be applied in the food industry and public catering

Sanitary cleaner // 2129145
The invention relates to hygienic cleaning tools designed for effective removal of resistant formations rust, sediment, hardness salts with toilets, porcelain sinks and tile surfaces
Cleaner // 2194071
The invention relates to household chemicals and can be used for cleaning cookers, sinks, tubs, toilets, tile, plastic
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