MXPA99004065A - Highly branched primary alcohol compositions, and biodegradable detergents made therefrom - Google Patents

Abstract

There is provided a new branched primary alcohol composition and the sulfates, alkoxylates, alkoxy sulfates and carboxylates thereof exhibiting good cold water detergency and biodegradability. The branched primary alcohol composition has an average number of branches per chain of 0.7 to 3.0, having at least 8 carbon atoms and containing both methyl and ethyl branches. The primary alcohol composition may also contain less than 0.5 atom%of quaternary carbon atoms, and a significant number of ethyl branches, terminal isopropyl branches, and branching at the C 3 position relative to the hydroxyl carbon. The process for its manufacture is by skeletally isomerizing an olefin feed having at least 7 carbon atoms or by dimerising a C 6-C 10 olefin, followed by conversion to an alcohol, as by way of hydroformylation, and ultimately sulfation, alkoxylation or both to obtain a detergent surfactant. Useful skeletal isomerization catalysts include the zeolites having at least one channel with a crystallographic free diameter along the x and/or y planes of the [001]view ranging from 42 to 70 nanometer. Useful dimerisation catalysts include a combination of a nickel carboxylate with an alkyl aluminium halids, or a combination of a nickel chelate with an alkyl aluminium alkoxide.

Description

COMPOSITIONS OF HIGHLY BRANCHED PRIMARY ALCOHOLS, AND BIODEGRADABLE DETERGENTS MADE FROM THESE Field of the Invention The invention pertains to a new composition of primary alcohol and the alkoxylates, sulfates and alkoxysulfates thereof and to their production and uses.

Background of the Invention The long chain olefin alcohols, especially those having from 10 to 28 carbon atoms, have considerable commercial importance in a variety of applications including detergents, soaps, reagents, and substances that lower the freezing point in lubricating oils. These alcohols are produced by any commercial process, such as oxo or hydroformylation of long chain olfins. The long chain alcohols typical are the commercially available alcohols NEODOL REF .: 29900 made by Shell Chemical Company, the EXXAL alcohols available from Exxon Chemical, and the LIAL alcohols available from Enichem (NEODOL, EXXAL and LIAL are registered trademarks).

In the manufacture of the NEODOL alcohols, a predominantly linear olefin feed is subjected to hydroformylation by reacting carbon monoxide and hydrogen in the olefin in the presence of an Oxo catalyst to form an alcohol. More than 80% of the number of alcohol molecules in the resulting composition are linear primary alcohols. Of the branched primary alcohols in the composition, substantially all, if not all, of the branching is at the hydroxyl-related carbon atom C2 carrying the carbon atom. These alcohols can subsequently be converted to anionic or non-ionic detergents or reagents in general by sulfonation or ethoxylation, respectively, of the alcohol. Alcohol ethoxysulfates are also known as anionic reagents for detergents.

The linear alcohol NEODOL has met with considerable commercial success with detergents because the NEODOL alcohol compositions can be produced commercially with high yields of linear alcohols. There is a desire to use the linear alcohols as intermediates for detergent reactive grade because it is generally recognized that the linear biodegradable alcohols, while the sulfonates of branched long chain alcohols exhibit low biodegradability. Since the detergents and soaps used by consumers for washing are currently released into the environment, the need to provide a reagent or detergent which is biodegradable is well recognized.

For example, US Pat. No. 5,112,519 describes the manufacture of a reagent by oligomerizing C3 and C olefins by means of a ZSM-23 surface-deactivated catalyst to form oligomers, hydroformylating the oligomer, and recovering a semilinear alcohol composition having less than 1.4. methyl branches, and these branches are limited to methyl branches. The alcohol can be ethoxylated and / or sulphated and is reported to be biodegradable, and also has improved properties at low temperature compared to isotridecyl alcohol. Retaining the linearity of the alcohol composition to less than 1.4, together with the methyl branches obtained, were important considerations in achieving a biodegradable reagent. It would be desirable, however, to obtain a biodegradable reagent without limiting the branching to methyl branches, without limiting the branching to less than 1.4, and without limiting oneself to the deactivated surface ZSM catalyst 23. It would also be desirable to make a biodegradable reagent without conducting oligomerization reactions through zeolite catalysts, which are expensive and can coke or be used quickly if one needs to build long chains by means of the catalyst.

Another product, EXXAL 13, is derived from the oligomerization of propylene by means of acid catalysis in a wide range of mono olefins, the range has an average of 13 carbon atoms that is distilled, but containing some olefins in the range of C10-15. The olefin is then subjected to hydroformylation using an oxo process. It is reported that EXXAL 13 is a 3-4 branched tridecyl methyl alcohol known for its use in lubricants and in those formulations of detergents that do not require rapid biodegradation. This is because the EXXAL 13 only biodegrades slowly. Since a large number of ramifications are not necessary, it would be desirable to make a reagent that has a greater amount of branching in the detergent formation is nevertheless easily biodegradable.

US Pat. No. 5,196,625 discloses a dimerization process for producing linear and / or mono-branched Cι to C 28 olefins using dimerization catalysts for the production of biodegradable alkyl benzene sulphonates by alkylating the olefins in the benzene. No mention is made of the use of dimerized olefins to make alcohols. Furthermore, the reported patent generally recognizes that "linear and mono-branched alkylaromatic sulphonates are generally much easier to biodegrade than multiramified alkylaromatic sulfonates, and therefore, much more desirable as detergents". For this reason, the patent seeks to ensure that the olefins made were substantially linear and mono-branched. Again, it would be desirable to make highly branched products that have good detergency and biodegradability of the alcohols, and also without considering limitations on the amount of ramifications that is less.

Those responsible for US Pat. No. 4,670,606 likewise recommend using "linear oxoalcohol detergents or those in which a linear fraction is as large as possible" for reasons of biodegradability in the detergent field, while oxo alcohols that are Highly branched oils are desirable as lubricating oil additives because the branching lowers the freezing point of the lubricating oil. Thus, the invention focused on methods for separating the two forms of a mixture.

The desire to make alcohols with highly branched high molecular weight defins in the Patent was also expressed.

North American 5,488,174. In discussing the problems found in the hydroformylation of olefins catalyzed by cobalt carbonyl, the patent leaders noted that this process produces a composition which contained branched compounds when initiated with internal olefins, which was particularly undesirable due to its poor biodegradability . Thus, those responsible for the patent recommend using catalytic processes which would produce mixtures that exhibit high branching / linearity ratios.

As previously noted, the line of highly linear NEODOL alcohol intermediates for the production of reactive detergents are commercially successful, in part due to the high linearity formation of these readily biodegradable. However, the high degree of linearity also increases the hydrophobicity of the hydrophobic part of the chain, thereby decreasing its solubility in cold water / detergency. In general, sulfates of highly linear alcohols suffer from low solubility in cold water / detergency. Along with the concern to use biodegradable compounds, government regulations also seek to reduce washing temperatures.

Thus, there is a growing need for alcohol intermediates which are biodegradable and exhibit good detergency at cold wash temperatures. The solution to this problem was not as simple as increasing the branching of the high molecular weight alcohols in order to decrease the hydrophobicity and through this the increase of the detergency in the water at low temperature is expected, due to the fact that I notice that it is previously known that branched compounds exhibit poor biodegradability.

Brief description of the invention.

New compositions of branched primary alcohols and their derivatives of alkoxylates, sulfates and alkoxysulfates have been found, which satisfy the requirements of biodegradability and detergency in cold water, and the processes for the production of these compositions.

The present invention therefore first relates to a branched primary alcohol composition, having from 11 to 36 carbon atoms and an average number of branches per molecule from 0.7 to 3.0, said branching comprising methyl and ethyl branches.

The invention relates in the second level to a process for the preparation of said branched primary alcohol composition, this process comprises the steps of: a) contacting an olefin feed comprising olefins having at least 7 carbon atoms with a catalyst effective to skeletally isomerize said linear olefin to produce a branched olefin of the same number of carbons; Y b) converting said branched olefin to said primary alcohol composition.

The term "skeletal isomerization", as used herein, refers to the hydrocarbon isomerization wherein the straight chains are converted, at least in part, to branched chains of the same number of carbon atoms. The catalyst of step a) is preferably a zeolite having at least one channel with crystallographic free diameter with a range from 0.42 to 0.70 nanometers. The conversion to alcohol in step b) is preferably by hydroformylation.

The invention relates thirdly to a different process for preparing said branched primary alcohol composition having from 13 to 21 atoms, these processes comprise of: adjusting, in the presence of a homogeneous dimerisation catalyst, an olefin feed comprising an olefin of C 6 -C 0 to produce a branched olefin Ca 2 -C 20; Y b) converting said branched C? 2-C2o to said branched primary alcohol composition.

The olefin feed of step a) is preferably linear olefin comprising at least 85% by weight C C-Cι olefins. Step a) is preferably a one-step dimerization process. The homogeneous catalyst preferably comprises a mixture of nickel carboxylate or a nickel chelate, with an alkylaluminum halide or an alkylaluminum alkoxide. Optionally, the branched olefin produced in step a) is subjected to a double bond isomerization step before going to step b). The conversion to alcohol in step b) is preferably by hydroformylation.

The invention relates in the fourth place to a composition of a branched primary alcohol alkoxylate, prepared by reacting said branched primary alcohol composition with an oxirane compound.

The invention relates in the fifth place to a composition of a branched primary alcohol sulfate, prepared by sulfating said branched primary alcohol composition.

And sixthly, the invention relates to a detergent composition comprising: a) one or more reagent (s) selected from the group of said alkoxylates of branched primary alcohols, branched primary alkyl sulfates, and branched alkoxylated primary alkyl sulfates; b) an intensifying agent; Y c) optionally one or more additives selected from the group of agents that control the foam, enzymes, bleaching agents, hydrotropes and stabilizers.

Detailed description of the invention As used herein, the phrase "average number of branches per molecular chain" refers to the average number of branches per molecule of alcohol, as measured by Nuclear Magnetic Resonance 13C (13 C NMR) as discussed below. The average number of carbon atoms in the chain is determined by gas chromatography.

Different references will be made for any specification and claims on the percentage of branches in a given carbon composition, the percentage of branching based on the types of branches, the average number of branches, and the percentage of quaternary atoms. These quantities will be measured and determined by using a combination of the following three 13C NMR techniques. (1) the first is the standard reverse trajectory technique using a 13 C peak 45 degree pulse and 10 s recycle delay (an organic free radical relaxation agent is added to the branched alcohol solution in deuterated chloroform to ensure the quantitative results). (2) The second is an E-Rotated J-Modulated NMR technique (JMSE) using a 1 / J delay of 8 ms (J is the coupling constant of 125 'Hz between the carbon and the proton for these aliphatic alcohols). This sequence distinguishes carbons with an odd number of protons of these carry an even number of protons, for example, CH3 / CH vs CH2 / Cq (Cq refers to a quaternary carbon). (3) The third is the "single cuat" NMR technique JMSE using a delay of 1 / 2J of 4 ms which produces a spectrum containing signals from only the quaternary carbons. The JSME single-cu in NMR to detect quaternary carbon atoms is sensitive enough to detect the presence of as little as 0.3% of quaternary carbon atoms. As an optional step, if one wishes to confirm a satisfactory conclusion of the results of a JSME single-NMR spectrum, one can also run a DEPT-135 NMR sequence. We have found that the NMR sequence DEPT-135 is very useful in the true differentiation of the quaternary carbons of the protonated carbons by means of separation. This is due to the fact that the DEPT-135 sequence produces the spectrum "opposite" to the JMSE "just cuat" experiment. While all the signals are then canceled exclusively from the quaternary carbons. The combination of the two spectra is therefore very useful in supporting no quaternary carbon in the JMSE "only cuat" spectrum. When referring to the presence or absence of quaternary carbon atoms through this specification, however, we say that the given amount or absence of quaternary carbon is a measure for the JSME single NMR method. If one wishes to optionally confirm the results, then the DEPT-135 technique is also used to confirm the presence and quantity of a quaternary carbon.

The detergency evaluations and how it was used through this were based on a test of the development of Redepositing the solid / detergency of high density laundry powder (HDLP). The evaluations in the working examples originated using radiotracer techniques from the Shell Chemical Company at temperatures designated in Table III with a water hardness of 150 ppm of CaCO3 (CaCl2 / MgCl2 = 3/2 on a molar basis). The sulfated primary alcohol compositions of the invention were tested, in a 1/4 base cup, against multisebum, cetanescualen and permanently solidified clay pressed with 65/35 polyester / cotton fabric (PPPE / C). The HDPL were tested at 0.74 g / l concentration, which contains 27% by weight of the sulfated primary alcohol composition, 46% by weight of enhancing agent (zeolite-4A), and 27% by weight of sodium carbonate.

The composition of the radiolabelled multisebum solid was as follows: Compound Et iquet; a% by weight Cetane 3H 12. 5 Squalene 3H 12. 5 Trisearin 3H 1 0 Arachis oil (peanuts) 3H 20 Cholesterol 14C 7 Octadecanol 14C 8.0 Oleic acid 14C 15.0 Stearic acid 14C 15.0 A Terg-O-Tometro was used to wash the samples at 15 minute intervals. The washing conditions were exposed to measure both the detergency in cold water at 10 ° C and the detergency in hot water at 36 ° C. The stirring speed was 100 r.p.m. Once the solid samples of the 4"x 4" radiotracer were washed by the Terg-O-Tometro, they were rinsed manually. The washing and rinsing water was combined to perform a measurement of solid sebum removed. The samples were counted to measure the clay removed.

For details concerning detergency methods and radiotracer techniques, reference may be made to B.E. Gordon, H.

Rodde ig and W.T. Shebs, HAOCS, 44: 289 (1967), W.T. Shebs and B.E. Gordon, JAOCS, 45: 377 (1968), and W.T. Shebs, Radioisotope Tecniques in Detergency, Chapter 3, Marcel Dekker, New York (1987).

The biodegradation test methods for measuring the biodegradability of sulfate working samples were performed in accordance with the test methods established in 40 CFR S796.3200, also known as the OECD 301D test method. By a biodegradable primary alcohol sulfate composition or reagent is meant that the compound or composition gives a measured biochemical oxygen demand (BOD) of 60% or more within 28 days, and this level must increase within 10 years of biodegradation that - exceeds 10 percent.

. The primary alcohol composition of the invention contains an average chain length per molecule in the range of 11-36 carbon atoms. For different applications of the reagents, such as detergents, the alcohol composition contains a carbon chain length of 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or 21 carbon atoms, or any decimal between these, expressed as an average within the range of 11 to 21 carbon atoms. The number of carbon atoms includes carbon atoms along the main chain as well as branched carbons.

Preferably, at least 75% by weight, more preferably, at least 90% by weight of molecules in the primary alcohol composition have chain lengths from 11 to 21, even more preferably from 14 to 18 carbon atoms. As a feature of the invention, the average number of branches is at least 0.7, as defined and determined above. The composition has an average number of branches of at least 1.5, in particular in the range from 1.5 to approximately 2.3, especially from 1.7 to 2.1, achieving a good detergency balance in cold water and biodegradability when sulfated. Conventional linear alcohol sulfates contain an average number of branches of only 0.05 to 0.4, and are quite biodegradable. At this point, however, the introduction of a high degree of branching for the purpose of increasing detergency in cold water has led to failures in the biodegradability tests. The composition of the primary alcohol of the invention, when sulfated, has the advantage of introducing a large number of branches to improve its properties in cold water without sacrificing biodegradability. Properties in cold water are improved when the number of branches is at least 1.5.

A feature of the invention lies in the provision of a primary alcohol composition as defined above, which has less than 0.5% Cq atoms as measured by a modified 13C NMR JMSE only cuat having a detection limit of 0.3 % of atoms or better, and preferably a primary alcohol composition which does not contain Cq by this NMR technique. For reasons not yet clearly understood, it is believed that the presence of Cq in an alcohol molecule prevents the biodegradation of this particular sulfated molecule by biological organisms. Alcohols containing as little as 1% Cq atoms have been found to biodegrade at failure rates. It is also believed that previous attempts at the introduction of a high degree of branching has led to the formation of a sufficient number of Cq to explain the failure of biodegradation.

In a preferred embodiment of the invention, less than 5%, or more preferably less than 3%, of the alcohol molecules in the primary alcohol composition are linear alcohols. The effective reduction in the number of linear alcohols to a small amount in the composition results from introducing branches in an olefin feed by skeletal isomerization. or dimerization technique using efficient catalysts as will be described below, instead of • introduce branches by methods such as acid-catalyzed oligomerization of propylene molecules, or oligomerization techniques catalyzed by zeolite. In a more preferred embodiment, the primary alcohol composition contains less than 3% linear alcohols. The percentage of molecules which are linear can be determined by gas chromatography.

When the branch has been reached by the. Skeletal isomerization, the composition of the primary alcohol of the invention can be characterized by the NMR technique while having from 5 to 25% branching at the C2 carbon position, relative to the carbon atom of the hydroxyl '. In a more preferred mode, from 10 to 20% of the number of branches are in the C2 position, as determined by the NMR technique. The primary alcohol composition also generally has from 10% to 50% of the number of branches at the C3 position, also determined by the NMR technique. When coupled with the number of branches seen at position C2, the primary alcohol composition in this case contains significant amounts of branching at the C2 and C3 carbon positions.

Not only the composition of the primary alcohol of the invention has a significant number of branches at positions C2 and C3, but we have also seen that the NMR technique of several primary alcohol compositions has at least 5% of the terminal branching type of branches. isopropyl, methyl branching media in the second to the last carbon position. We have seen at least 10% of the isopropyl-terminal type branches in the primary alcohol composition, typically in the range of -105 to 20%. In the hydroformylated olefins of the NEODOL series, less than 1%, and usually 0.0%, of the branches are terminal isopropyl branches. By skeletal isomerization the olefin according to the invention, however, the primary alcohol composition contains a large percentage of terminal isopropyl branches relative to the total number of branches.

Considering the combined number of branches that occur in C2, C3, and the isopropyl positions, there are embodiments of the invention where at least 20%, more preferably at least 30%, of the branches are concentrated in these positions. The scope of the invention, however, includes ramifications that occur across the length of the main carbon structure. In another preferred embodiment of the invention, the total number of methyl branches at least 40%, even at least 50%, of the total number of branches, as measured by the NMR technique described above. This percentage includes all the numbers of methyl branches seen by the NMR technique described above within the carbon compositions of Ci to C3 relative to the hydroxyl group, and the terminal isopropyl of the methyl branching type.

Significantly, we have consistently observed a significant increase in the number of ethyl branches on those seen in NEODOL alcohols. The number of ethyl branches can be in the range from 5% to 30%, more typically from 10% to 20%, based on all types of branches detected by the NMR method.

Thus, the skeletal isomerization of olefins produced with both methyl and ethyl branching, and these alcohols, when sulfated, alkoxylated, or both, worked extremely well in biodegradability and detergency tests. Thus, the types of catalysts that one uses can develop skeletal isomerization is not restricted to those which will produce only methyl branching. The presence of a variety of types of branches is believed to increase a good overall balance of properties.

The olefins used in the feed of defines for the skeletal isomerization are at least C0 mono olefins. In a preferred range, the olefin feed comprises C0 to C35 mono olefins. Olefins in the range of Cu to Cig are • considered more preferred for use in the present invention, to produce primary alcohol compositions in the range of Ci2 to C20, which are the most common ranges for detergent applications. As a general rule, the largest number of reactive derivative carbons, 'the most notable s < pn improvements in. the physical properties and the ability to formulate them.

In general, the olefins in the feed composition are predominantly linear. Attempting to process a predominantly branched olefin feed, which contains quaternary carbon atoms or extremely branched lengths, would require separation methods after passing the define current through the catalyst bed to separate these species from the desired branched olefins. While the olefin feed contains some branched defines, the olefin feed processed by the skeletal isomerization preferably contains more than 50 percent, more preferably more than about 70 percent, and more preferably more than 80 mole percent or more of the molecules of olefin linear.

The olefin feed generally does not consist of 100% olefins within the specified carbon number range, as it is not commercially available pure. The olefin feed is usually a distribution of mono olefins having different carbon lengths, with at least 50% by weight of the defines that are within the range or digit of the carbon chain, however specified. Preferably, the olefin feed will contain more than 70% by weight, more preferably about 80% by weight or more of mono olefins in a range of the number of carbons specified (e.g., C7 to Cg, Cio to C? 2, Cu to C15, C12 to Cx3, C15 to C? 8, etc.), the rest of the product that is olefin of another carbon number or structure of carbons, diolefins, paraffins, aromatics, and. other impurities resulting from the synthesis process. The placement of double bonds is not limited. The olefin feed composition may comprise α-olefins, internal olefins, or a mixture thereof.

The Alfa Olefinas Chevron product series (registered trademark and sold by Chevon Chemical Co.), predominantly produces linear olefins by the thermal separation of paraffin waxes. The commercial olefin products manufactured by the ethylene oligomerization. are sold in the United States of America by the Shell chemical Company under the trademark NEODENE and by Ethyl Corporation as Ethyl Alpha-Olefins. Specific procedures for preparing suitable linear olefins from ethylene are described in US Pat. Nos. 3,676,523, 3,686,351, 3,737,475, 3,825,615 and 4,020,121. While most olefin products are largely comprised of alpha olefins, highly linear internal olefins are also produced, for example, by the chlorination dehydrochlorination of paraffins, by dehydrogenation of paraffins and by isomerization of alpha olefins. The products of linear internal olefins in the range of C8 to C22 are sold by Shell Chemical Company and by Liquichemica Company.

The catalyst used for skeletal isomerization preferably contains a zeolite having at least one channel with a free crystallographic channel diameter in the range of 0.42 to 0.70 nanometers, measured at room temperature, with essentially no channel present which has a free channel diameter which is greater than 0.70 nanometers.

The skeletal isomerization catalyst must contain at least one channel having a free crystallographic diameter at the entrance of the channel within the established range. The catalyst must not have a diameter at the entrance of the channel which exceeds the upper limit in the range of 0.70 nanometers. Zeolites having channel diameters greater than 0.7 nm are susceptible to undesirable aromatization, oligomerization, alkylation, coking and formation of by-products. On the other hand, if the zeolite does not contain a channel having a free diameter along the x-plane or at least 0.42 nm, the size of the channel becomes so small as to allow diffusion of the olefin into and out of the channel pore. once the olefin becomes branched. Thus, the zeolite must have at least one channel with free diameters than the channel within the range of 0.42 to 70 nm. All other specifications are preferred.

Without joining the theory, it is believed that the olefin molecule, due to its long carbon chain, does not have to enter the zeolite channel, diffuse through it, and exit through the other end of the channel. The rate of branching is seen when the olefin feed passes through the zeolite does not correspond to the theoretical rate of branching if each olefin molecule has passed through the channels. Rather, it is believed that most olefins partially penetrate the channel by an effective distance to branch the portion of the chain into the channel, and subsequently without leaving the channel once it is isomerized. In this case, the olefin molecules. in the composition they would predominantly have a structure which is branched at the ends of the main structure of the carbon chain of the olefin, and substantially linear towards the center of the molecule, for example, at least 25% of the carbons in the center are without ramifications. The scope of the invention, however, includes branching along the entire carbon chain within the parameters described above with respect to the molecular structure.

Preferred embodiments of the zeolite structure are described in U.S. Patent No. 5,510,306. The structure of the zeolite is also described in the Atlas of the Types of the Zeolite Structures, by W. M. Meier and D.H. OlsonY With respect to the structure, in a preferred embodiment, the catalyst contains a channel having free diameters within the range greater than 0.42 nm to less than 0.70 nm in length both in the x and y planes in the view [001]. Zeolites with these specific channel sizes are typically referred to as medium or intermediate channel • zeolites and typically have a ring channel structure the 10-T member (or shirred member 12-T) in view of a 9-T member or minor (smaller pore) in another opinion. There is no limit for the number of channels or their orientation (parallel, intersections not interconnected, or interconnected at any angle) in the zeolite. There is also no limit on the size of the channels which are outside the range established in both planes x and y, provided that the other channels have no free diameter in the x or y planes and which is greater than 0.70 nm. For example, other channels have a free diameter of 0.42 nm or less in one or both x and are within the scope of the invention.

There is also no limit on the number of dimensions, which can have the channel system one, two, or three. While the scope of the invention includes two or three dimensional zeolites with interconnected channels that are any size smaller than 0.70 nm, and includes at least one channel within the established range, there may be limited circumstances where, for example, α-olefins They can be found at the intersection of the intersecting channels and dimerize or oligomerize, depending on the size of the olefin, the proximity of the intersection that is interconnected to the channel entries, the size of the intersection that is interconnected, the size of the interconnecting intersection, temperature, flow velocity, among other factors. It is unlikely that this dimer would back off the diffusion into the zeolite, in dimer it can coke the catalyst or break it into the channel structure, forming by-products of olefins having quaternary carbon branches. Thus, the system of channels that are interconnected in a • two- or three-dimensional zeolite must have effective free diameters to prevent the formation of dimers, trimer, or oligomers under the given processing conditions, which when thermally broken, can produce Branched quaternary byproducts. In a preferred embodiment, all channels that are interconnected to the channel within the established range have free diameters in both planes x and y and 0.42 nm or less in order to eliminate the possibility of two olefin molecules coming into contact with each other inside. of the zeolite and dimerize or trimerize. This preference, however, applies only to the interconnection channel. A zeolite containing more than one channel, if one, two or three dimensions or even intersect in different planes, but none of which are interconnected, does not increase the possibility of dimerization or trimerization because the channels do not connect. Thus, there is no preference for these types of structures, provided that the basic requirements noted above are observed.

Examples of zeolites, including molecular sieves, that can be used in the processes of this invention with a channel size between 0.42 and 0.70 nm, include ferrierite, A1P0-31, 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, lamountite, cancrinite, ofretite, forms of hydrogen of stiblite, the magnesium or calcium form of mordenite and parteite. The isotypic structures of these structures, known under other names, are considered to be equivalent. In another view describing the compositions of the structures of several of these zeolites is provided in the New Developments in Zeolite Science Technology, "Aluminophosphate Molecular Sierves and the Peridic Table", Flanigen et al. (Kodansha Ltd., Tokyo, Japan 1986).

Different natural zeolites such as ferrierite, healandite and stilbite have a structure with a uni-dimensional pore with a pore size or slightly smaller than 0.42 nm in diameter. These same zeolites can be converted into zeolites with channel sizes greater than those desired by removing the associated alkali metal or alkaline earth metal by methods known in the art, such as ammonium ion exchange, optionally followed by calcination, to produce the zeolite. in substantially its hydrogenated form. See, for example, US Pat. Nos. 4,795,623 and 4,942,027. - Placing the alkaline or alkaline earth metal associated with the hydrogenated form that corresponds to increasing the diameter of the channel. It is understood that the diameter of the channel or "size" means that the diameter or size of the channel is effective for diffusion. Alternatively, natural zeolites with too large channel sizes, such as those forms of mordenite, can be altered by substituting the alkali metal with large ions, such as larger alkaline earth metals to reduce the size of the channel and thus become useful for the processes of this invention.

Particularly preferred zeolpta are those which have the structure of the isotypic network of ferrierite (or homotypic). See the Atlas of Zeolite Structure Types, by W. M. Mier and D.H. Olson, published by Butterworth-Heinemann, third revised edition, 1992, page 98. The prominent structural features of ferrierite found by X-ray crystallography are parallel channels in the aluminosilicate network which are grossly elliptical in cross-section. Examples of zeolites having the isotypic structure of ferrierite include natural and synthetic ferrierite (may be ortho-or monoclinic), Sr-D, FU-9, (EP B-55,529), ISI-6 (US Patent No. 4,578,259), Nu-23 (E.P. A-103,981), ZSM-35 (North American Patent No. 4,016,245), ZSM-38 (North American Patent No. 4,375,573). The hydrogenated form of ferrierite (H-ferrierite) is the most preferred zeolite and is considered to be substantially of one dimension, having parallel running channels, with elliptical channels having free diameters of 0.42 x 0.54 nm along the planes xyy in the estimation [001], which are totally long to allow the entrance of the linear olefin and the exit diffusion or through the channel of the branched isoolefin with methyl and so small to retard the formation of coke. Methods for preparing various H-ferrite are described in US Patent Nos. 4,251,499, 4, 795, 623, and 4, 942, 027.

The skeletal isomerization catalyst used in the isomerization process of this invention can be combined with a refractory oxide that serves as a binding material. Suitable refractory oxides include natural clay, such as bentonite, montmorillonite, attapulgite, and kaolin; alumina, silica, silica-alumina; hydrated alumina; titania; zirconia and mixtures of these. The weight ratio of zeolite to the binding material has suitable ranges from about 10:90 to about 99.5: 0.5, preferably from about 75:25 to about 99: 1, more preferably from about 85:15 to about 95: 5. (anhydrous base).

Preferably the support material, for example, selected from the silica or aluminas, the silicas-aluminas and the clays. The most common support materials are aluminas, such as pseudoboehmite, gamma aluminas and bayerite. These support materials are easily commercially available and are • used for. the manufacture of alumina-based catalysts. LaRoche Chemicals, through its VERSAL family of aluminas and Vista Chemical Company, through its CATAPAL aluminas, provides suitable alumina powders which can be used as support materials when preparing the current catalyst (VERSAL and CATAPAL are registered trademarks). The preferred alumina support materials for use in catalyst preparation, particularly when extrusion is used, are highly dispersible alumina powders. These highly dispersible aluminas t have a dispersion greater than 50% in an aqueous acid dispersion having an acid content of 0.4 milligrams equivalents of acetic acid per gram of A1203. These highly dispersing aluminas are exemplified by the CATAPAL D alumina of view.

Preferably, the skeletal isomerization catalyst is also prepared with at least one selected acid. of monocarboxylic acids and inorganic acids and at least one organic acid with at least two carboxylic acid groups ("polycarboxylic acid"). Preferably monocarboxylic acid includes monocarboxylic acid having substituted or unsubstituted hydrocarbyl groups having 1 to 20 carbon atoms which may be aliphatic, cyclic or aromatic. Examples include acetic acid, formic acid, propionic acid, butyric acid, acid caproic, glycolic acid, lactic acid, hydroxybutyric acid, hydroxycyclopentanoic acid, salicylic acid, mandelic acid, benzoic acid, and fatty acids. 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 adhered through a carbon-carbon bond to a hydrocarbyl segment. The link may be in any portion of the hydrocarbyl segment. The polycarboxylic acid preferably has a hydrocarbyl segment from 0 to 10 carbon atoms which may be aliphatic, cyclic or aromatic. The hydrocarbyl segment has 0 carbon atoms by oxalic acid with two carboxylic acid groups attached through a carbon carbon bond. Examples of polycarboxylic acids include, for example, tartaric acid, citric acid, malic acid, oxalic acid, fumaric acid, itaconic acid, italic acid, phterephthalic acid, phenolmalonic acid, hydroxyphthalic acid, dihydroxyfenaric acid, tricarballylic acid, benzene-1 acid, , 5-tricarboxylic acid, isocitric acid, mucic acid and glucaric acid. The polycarboxylic acids can be any isomer of the above acids or any stereoisomer of the above acids. More preferred are polycarboxylic acids with at least two carboxylic acid groups and at least one hydroxyl group. The second most preferred acids (eg, polycarboxylic acids) are citric acid, tartaric acid and malic acid.

Optionally, the metals that promote the oxidation of the coke can be incorporated in the current catalysts to promote the oxidation of the coke in the presence of oxygen at a temperature higher than 250 ° C. While the term "metal (s)" is used herein in reference to the oxidation catalysts, these metals will not necessarily be in the zero-valent oxidation state and in different cases will be at higher oxidation states. Thus, the "metal (s)" can be surrounded by oxides as well as metals. Preferably the metal (s) which promotes the oxidation of the coke used are transition metals and rare earths. More preferably metals promoting coke oxidation are selected from groups IB, VB, VIB, VIIB, and VIII of the transition metal series of the periodic table. Specifically preferred are Pd, Pt, Ni, Co, Mn, Ag, and Cr. More preferably, the metals of Group VIII are palladium and / or platinum. The amount of metal introduced can be up to about 2% by weight, measured as the metal by the total weight of the catalyst. When platinum and / or palladium is used, it is more preferable to incorporate smaller amounts instead of large amounts of metals in the support material / zeolite. Preferably platinum and / or palladium will be in the range of 5 to 3000 ppm by weight, metal base, of the final catalyst.

In a preferred method, the present catalysts can be prepared by mixing a mixture of at least one zeolite as defined herein, a support material containing alumina, water, at least one monocarboxylic acid or inorganic acid and at least one polycarboxylic acid in a container or a container, which forms granules of the mixture and the granules are calcined at elevated temperatures. In a preferred embodiment of the zeolite powders and alumina-containing powders are mixed with water and one or more of the monocarboxylic acid or inorganic acid (first acid) and one or more of the polycarboxylic acid (second acid) and optionally one or more metal compounds that promotes the oxidation of the coke and the resulting mixture (paste) is formed into granulates. The metal that promotes the oxidation of the coke can alternatively be impregnated.

Preferably the granule is formed by extrusion but can also be formed in catalytically useful form by hydrostatic or mechanical pressure by pressing on the die or mold.

When the extrusion is used, optionally the cellulose derivatives help, for example, METHOCEL F4M hydroxypropyl methylcellulose (METHOCEL is a registered trademark), it can be used (manufactured by Dow Chemical Company). The term "granules" is used here as it can be any shape or form as large as the materials are consolidated. The formed granules are calcined in a range of temperatures from a lower range from 200 ° C, preferably from 300 ° C, more preferably from 450 ° C, up to an upper range of up to 700 ° C, preferably up to 600 ° C, more preferably up to 525 ° C.

The ratio of the first acids to the second acids is preferably within the range of 1:60 to 60: 1, more preferably 1:10 to 10: 1. The amount of the first acid used is within an amount effective to peptize the mixture. Preferably the amount of the first acid is from 0.1 to 6 weight percent, more preferably from 0.5 to about 4 weight percent based on the combined weight of zeolite and the support material containing alumina (anhydrous solid base). Aluminas with lower dispersibility than Vista's CATAPAL D may require higher amounts of acid to peptize these. The amount of the second acid is in an amount effective to promote the catalytic activity of the catalyst which is from 0.1 to 6, preferably from 0.2 to 4 weight percent based on the combined weight of zeolite and the support material containing alumina (anhydrous solid base).

The mixture is mixed vigorously and vigorously until the mixture appears uniform. The mixture can be developed by combining all the compounds of the mixture at one time or by adding the compounds of the mixture to different mixing stages. Mixing can be achieved by mixing powders. The term "powder mixing" is used herein as a means of mixing powders to which sufficient water has been added to form a sticky part and where mixing is achieved by cutting the dough. Commercially available mixers such as the Lancaster Mix Muller and the Simpson Mix Muller can be used to perform the mixing. A commercial mixer such as mixing tape and / or power mill can also be used to perform mixing.

Optionally the metal that promotes the oxidation of the coke can be impregnated to form granules with a solution containing metals instead of mixing in the paste mixture.

The temperature at which the skeletal isomerization can be performed can be in the range from 200 ° C to 500 ° C. The temperatures must not exceed the temperature at which the olefin separates. Suitable pressures maintained during the isomerization reaction is in the partial pressure range of the olefin from 10 to 1000 kPa, more preferably from about 50 to 500 kPa, more preferably about 50 to 200 kPa.

High conversion, high selectivity, and high performance are achieved by the process of the present invention. The olefin feed comprises linear olefins having an average of at least 7 carbon atoms which are connected with an effective catalyst for skeletally isolating said linear olefins with a conversion of at least 40% in a single step. However, the process of the invention allows one to skeletally isomerize the linear olefins with much greater conversions. Conversions of at least 70%, preferably at least 80%, more preferably at least 95% are achieved in a single step in the process of the invention. Advantageously, the conversion percentages are obtained at temperatures ranging from 200 ° C to 500 ° C, preferably from 200 ° C to 350 ° C.

The catalyst used in the skeletal isomerization process is also highly selective for the manufacture of skeletally isomerized branched olefins. Although great selectivities are achieved according to the skeletal isomerization process, the selectivity of the catalyst for the manufacture of highly branched C7 defines from a stream of highly linear C7 olefins is at least 30% in one step since the process uses catalysts with low selectivities that are not sufficiently effective or economically justified. Selectivities greater than at least 70%, more preferably at least 80%, more preferably at least 90%, and even as high as at least 95%, are achieved in the process of the invention in one step.

Another advantage observed by skeletally isomerizing the C7 or highly linear olefin streams according to the process of the invention is that the high conversion of the linear olefin stream can be obtained in conjunction with the high selectivity with the skeletally isomerized branched defins. The olefin stream is preferably converted into percentages of at least 70%, with a selectivity for the skeletally isomerized branched olefins of at least 70%, more preferably at least 80%, • more preferably at least 90%. In another embodiment, at least 80% of the olefin stream is converted, with a selectivity for the skeletally isomerized branched olefins at least 80%, more preferably at least 90%, more preferably at least 95%. In another embodiment, at least 90% of the olefins are converted, with a selectivity of 90% for the skeletally isomerized branched olefins, more preferably at least 95% or greater.

The process of skeletal isomerization also produces high yields of skeletally isomerized branched olefins. The yield of the skeletally isomerized branched olefins should be at least about 10%, but yields of at least about 50%, more preferably at least about 65%, more preferably, more preferably at least about 80%, and even such highs as approximately 90%. The higher yield of obtained skeletally isomerized branched olefins is limited to olefins at the skeletal isomerization temperature.

The • current process of skeletal isomerization can be operated in a wide range of conditions. The olefin weight olefin speed space may be in the range from 0.1 to 100 per hour. Preferably, the WHSV is between 0.5 to 50, more preferably between 1 and 40, more preferably between 2 and 30 per hour. The lower WHSV, is the possible to operate at low temperatures while achieving high yields of skeletally isomerized branched defines. At large WHSV, the temperature is generally increased in order to maintain the desired conversion and the selectivity for branched defines is skeletally isomerized. In addition, optimum selectivities are generally achieved at low olefin partial pressures mentioned above. For this reason, it is often advantageous to dilute the feed stream with a diluting gas such as nitrogen or hydrogen. Although reducing the partial pressure of the olefin with a diluent may be beneficial to improve the selectivity of the process, it is not necessary to dilute the olefin stream with a diluent.

If a diluent is used, the olefin molar ratio with diluent may be in the range from 0.01: 1 to 5: 1.

When the branching has been achieved by dimerization, the primary alcohol composition of the invention has relatively few branched points at the position of carbon Ci to C3 relative to the hydroxyl carbon and few or no isopropyl termination, which is, little or no branched on the second to the last carbon atom along the main chain of the molecule relative to the hydroxyl carbon atom. In particular, the typical alcohol molecule in this case contains less than 25% branching at the C2 and C3 positions, and less than 5% isopropyl terminating, usually no isopropyl group has been detected.

From these carbon positions, alcohol molecules made from dimerized olefins look similar to NEODOL alcohols. However, other than NEODOL alcohols which are predominantly linear, the composition of the invention has a very high average number of branches per molecule. Due to the large number of branches found in the composition of the primary alcohol of the invention and the relatively low percentage of branches at the points at C2, C3, and the positions of the isopropyl terminal carbon, most of the branches are towards the center of the molecule, with a significant number of branches that are located on one or both of the dimerized carbon atoms. The NMR spectral data is consistent where the branches are thought to be localized based on a chemical reaction equation.

The types of branching found in the primary alcohol composition of the invention vary from methyl, ethyl, propyl, and butyl, or greater. A significant number of the branches detected by the NMR were ethyl groups, although this may vary depending on the composition of the feed and the reaction conditions. In one embodiment, however, the number of ethyl groups in the primary alcohol composition of the range of the invention, preferably, from 10% to 30%, which is a significant jump from the amount of ethyl groups detected in the NEODOL alcohols. . The number of methyl groups detected by NMR can also vary widely for the same reason. Typically, however, the number of methyl groups will range from 10% to 50%, as detected by NMR.

Clearly speaking, a primary alcohol composition is obtained by dimerizing an olefin feed comprising C6-C linear olefins or in the presence of a dimerization catlizer under dimerization conditions to obtain C2-C20 olefins. V In one embodiment, the olefin feed is at least 85 mol%, preferably at least 90 mol%, more preferably at least 95 mol% linear olefins. The rest of the olefin feed comprises only a low number of branched olefins, preferably less than 3 mol%.

The olefin feed can contain small or long olefins. In a preferred embodiment, however, the olefin stream also comprises at least 85% by weight of the C6-C? Olefins, or more preferably 90%, more preferably 95%, by weight of the Cß-Cio ole olefins. of the process of the invention is that one can make mixtures of both dimerized olefins the pairs and the nones in the feed, as distinguished from these processes which depend on the oligomerization of olefins C3 or C4 to build high molecular weight olefins.

The olefins feed can be made from internal or alpha olefins, or mixtures of these. Preferably, most of the olefins present in the feed comprise internal olefins because the dimerization of these olefins tend to produce a variety of the branched type, which are methyl, ethyl, and propyl ramifications, even butyl branches, by majority means that more than 50% by weight of the definition feed is comprised of internal olefins. More preferably, at least 75% by weight of the olefin feed is comprised of internal olefins.

In one embodiment of the invention, a one-step dimerization process is provided.

By a one-step dimerization process it is understood that an olefin feed, once dimerized, is not subject to dimerization. A one-step process, however, includes recycling the unreacted olefin feed to the dimerization zone because this unreacted olefin feed was not dimerized. Also included is a continuous process or several batch reactors operating in parallel, provided that a dimerized olefin stream is not fed to a subsequent dimerization reaction zone by a second or subsequent dimerization. This one-step process provides the advantage that one can use conventional olefin streams without the need for expensive and sophisticated extraction and separation processes to make a current of high purity linear defines. The olefin feed can be obtained by the conventional oligomerization of ethylene, which can subsequently be disproportionate, or by the Fischer-Tropsch process, which uses a 1-carbon oligomerization by passing CO and H2 over iron or cobalt catalyst; as distinguished from C3 or C olefin threery or tetramer feeds which are widely branched or require special extraction steps to obtain high linearity in the olefin feed.

Typically, the dimerization is carried out at temperatures in the range from about -10 ° C to 100 ° C, preferably from 1 to 5 hours, using an olefin to catalyze the molar ratio of 200 to 20,000, preferably 1,000 to 10,000 oleins of olefin. mol of catalyst. The dimerization is generally carried out as a liquid phase reaction using pressures in the range of 0 to 300 kPa, preferably 100 to 200 kPa. Where the dimerization is carried out with a batch process, the catalyst can conveniently be prepared in situ in the reactor. The dimerization can also be carried out as a continuous process, semi-batches, or multi-stages. It should be appreciated that where typically or preferably the process conditions (eg, temperature, times, catalyst ratios, etc.) have been given, other process conditions could also be used. The optimum process conditions (eg, temperature, time, reaction, reagent ratios, catalyst ratio, solvents, etc.) may vary with the particular reagents, the catalyst, or solvents used, but can be determined by the process of routine optimization.

The dimerization catalyst of this invention can be prepared by contacting the appropriate catalyst compounds in the olefin to be dimerized. Preferably, the catalyst compounds are not mixed together before their addition to the olefin feed, this can cause catalyst decomposition. The addition of solvents, such as chlorobenzene or cyclohexane, can be used and not decrease the development of the catalyst.

The selection of the catalyst for dimerization is one which is selective towards the manufacture of high yields of dimerized olefins having an average from 0.7 to 3.0 and preferably 0.9 to 2.0 branches per molecule. These catalysts are preferably soluble in hydrocarbon medium, for example, the olefin feed stream. Examples of hydrocarbon-soluble dimerization catalysts are complexes where a metal, preferably nickel, is attached to at least one halogenated aluminum compound. Another type of catalyst consists of the complex formed by mixing at least one nickel compound with at least one alkylaluminum compound and optionally a ligand, for example phosphine. These catalysts are well known in the art. Catalyst illustrations that can be used in this type of process are given in U.S. Patent Nos. 4,366,087; 4,326,650; and 4,398,049.

A preferred class of catalysts used in the process are homogeneous catalysts comprising a combination of a nickel carboxylate or a nickel chelate, with an aluminum halide or an alkylaluminum alkoxide, respectively. The mol ratio of Al / Ni is suitably from 1.0 to 20.0.

The nickel compound comprises a nickel carboxylate or a nickel chelate. The carboxylate of the nickel carboxylate can be represented by the formula (RCOO) 2Ni, where R is a hydrocarbyl radical, branched or unbranched, for example an alkyl, cycloalkyl, alkenyl, aryl, aralkyl or alkaryl radical, containing at least 2 atoms of carbon, preferably a sufficient number of carbon atoms to aid compatibility with the hydrocarbon medium, such as a hydrocarbyl radical of 5-20 carbon atoms, this radical can be substituted, for example, with hydroxyl groups. One of the RCOO- groups of the divalent nickel carboxylate mentioned above can optionally be substituted with the group represented by RiCOO-, where Ri is a halogenoalkyl radical containing from 1 to 3 carbon atoms, as described in US Pat. No. 4,366,087 .

Examples of the nickel carboxylates include, but are not limited to, nickel bis- (2-ethylhexanoate); 2-ethylhexanoate nickel trichloro (or trifluoro) acetate; 2-ethylhexanoate o-chlorobenzoate nickel; and acetonate of 2-ethylhexanoate nickel, nickel trifluoroacetate 2-ethylbutyrate, nickel trichloroacetate 2-ethylbutyrate, nickel trifluoroacetate 3, 3-dimethylbutyrate, nickel trichloroacetate 3, 3-dimethylbutyrate, nickel trifluoroacetate 4-methylvalerate, trifluoroacetate nickel heptanoate, nickel trichloroacetate heptanoate, nickel tribromoacetate heptanoate, nickel heptanoate triiodoacetate, nickel monofluoroacetate 2-ethylhexanoate, nickel trichloroacetate 2-ethylhexanoate, nickel dichloroacetate 2-ethylhexanoate, nickel monochloroacetate 2-ethylhexanoate, nickel triiodoacetate 2 -ethylhexanoate, nickel octoate trifluoroacetate, nickel octoate trichloroacetate, nickel decanoate trifluoroacetate, nickel decanoate trichloroacetate, nickel myristate trifluoroacetate, nickel palmitate trifluoroacetate, nickel trifluoroacetate dodecylbenzoate, nickel trichloroacetate diisopropylsalicylate, nitride pentafluoropropionate Nickel myristate and heptafluorobutyrate 2-ethylhexanoate.

The nickel chelate compounds, which react with alkylaluminum alkoxides, are described in US Pat. Nos. 3,424,815, and 4,959,491. Nickel chelates include aquiles that have the formula where R and R 'independently are hydrogen, alkyl or aryl of up to 10 carbon atoms, or haloalkyl or haloaryl of up to 10 carbon atoms, with the proviso that the two R' groups of each chelating ligand together with the carbon atoms adjacent to which they adhere, they can form a six-membered aromatic carboxylic ring of up to 4 halogen substituents. The halogenated chelating ligand preferably has up to 15 carbon atoms and from 2 to 8 halogen substituents, but preferably each month has up to 10 carbon atoms and from 3 to 6 halogen substituents. The halogen substituents of the chelating ligand are suitably fluoro, chloro, bromo, iodo, where the R 'groups together form a bivalent radical where the monoenol configuration is retained as part of the aromatic ring.

The aluminum compound comprises a hydrocarbylaluminum halide or a hydrocarbylaluminum alkaloid. The hydrocarbyl group generally comprises 0, 1 or 2 hydrocarbyl groups each having from 1 to 20 carbon atoms, usually from 1 to 12 carbon atoms, the groups including alkyl, aryl, aralkyl, alkaryl, and cycloalkyl. The halide comprises 1 to 6 halides, such as fluoride, iodide, chloride, or bromide, preferably any is readily available, such as chloride. Examples of the hydrocarbylaluminum halides include A1C13, dichloroethylaluminum, ethylaluminum sesquichloride, dichloroethylaluminum, dichloroisobutylaluminum, chlorodiethyl aluminum or mixtures thereof.

Suitable alkoxides may be 1 to 2 alkoxy groups these alkyl segments are defined above with respect to alkyl groups adhered to aluminum.

Optionally, the catalyst may also contain a small amount of water which has an effect of increasing the speed of the catalytic dimerization. Generally, the amount of water used will be an amount sufficient to increase the speed of the catalytic dimerization.

At the outlet of the reactor, the catalyst can be deactivated in a known manner, for example, with ammonia and / or an aqueous solution of sodium hydroxide and / or an aqueous solution of sulfuric acid, or an organic solution of acid / bicarbonate. The unconverted olefins and the alkanes, if any, are then removed from the oligomers by distillation, or any other suitable method, such as extraction and the like. The unreacted feed can be recycled to the initial feed.

The branching-skeletal isomerization or dimerization-olefins are subsequently converted to alcohols and to any wide range of reagents, including nonionic, anionic, cationic, and reactants to flowerbeds. The branched olefin serves as an intermediate reagent. Specifically, the branched olefin serves as the hydrophobic radical of the reactive molecule, while the radical is added to the olefin during the conversion process serving as the hydrophilic. Neither the particular reagent nor the means used to convert the branched olefin to an alcohol or reagent is considered critical to the present invention, this does not provide a rearrangement of the skeletal structure of the olefin to the extent that the byproduct is not very biodegradable, or reduces the degree of branching to less than 0.7.

The conversion of the branched defines to a primary alcohol composition is conveniently carried out, for example, by hydroformylation, by oxidation and hydrolysis, by sulfation and hydration, by epoxidations and hydrations, or the like. In hydroformylation, the skeletonically isomerized olefins are converted to alkanols by reaction with carbon monoxide and hydrogen according to the Oxo process. Most commonly the "modified Oxo process" is used, which uses cobalt or rhodium catalysts modified with phosphine, phosphite, arsine or pyridine ligands, as described in US Patent Nos. 3,231,621; 3,239,566; 3,239,569; 3,239,570; 3,239,571; 3,420,898; 3,440,291; 3,448,158; 3,448,157; 3,496,203; and 3,496,204; 3,501,515; and 3,527,818. The production methods are also described in Kirk Othmer, "Encyclopedia of Chemical Technology" 3rd De. Vol. 16, pages 637-653; "Monohydric Alcohols: Manufacture, Applications and Chemistry", E. J. Wickson, De. Am. Chem. Soc. 1981.

Hydrofortion is a term used in the art to denote the reaction of an olefin with CO and H2 to produce an aldehyde / alcohol which has one or more carbon atoms that the reactive olefin. Frequently, in the art, the term hydrofortion is used to cover the aldehyde and reduction to the total alcohol passage, for example, hydrofortion refers to the production of alcohols from olefins by means of carbonylation and an aldehyde reduction process. . As used herein, hydrofortion refers to the last production of alcohols.

Illustrative catalysts include cobalt hydrocarbon catalyst, phosphine-cobalt ligand catalyst, and phosphine-rhodium ligand catalyst. The choice of catalyst determines the different reaction conditions imposed. These conditions can vary widely, depending on the particular catalysts. For example, temperatures can range from approximately ambient temperatures to 300 ° C. When cobalt carbonyl catalysts are used, which are also typically used, temperatures will range from 150 ° C to 250 ° C. A person with ordinary skill in the art, when referring to the aforementioned references, or to any of the literature are well known in oxo alcohols can easily determine these conditions of temperature and pressure will be necessary to hydroformilate the dimerized olefins.

Typical reaction conditions, however, are moderate. Temperatures in the range of 125 ° C to 200 ° C are recommended. Reaction pressures in the range of 2170 to 10440 kPa are typical, however lower or higher pressures may be selected. The ratios of catalyst to olefin are suitable ranging from 1: 1000 to 1: 1. The ratio of hydrogen to carbon monoxide can vary widely, but is usually in the range of 1 to 10, preferably about 2 moles of hydrogen to a carbon monoxide template in favor of the alcohol product.

The hydrofortion process can be carried out in the presence of an inert solvent, although it is not necessary. A variety of solvents may be applied such as ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and cyclohexone; aromatic compounds such as benzene, toluene and the xylenes; halogenated aromatic compounds such as chlorobenzene and orthodichlorobenzene; halogenated paraffinic hydrocarbons such as methylene chloride and carbon tetrachloride; paraffins such as hexane, heptane, methylcyclohexane and isooctane and nitriles such as benzonitrile and acetonitrile.

With respect to the catalyst ligands, mention may be made of organotriary phosphines, such as trialkylphosphines, triamlyphosphine, trihexylphosphine, dimethylethylphosphine, dialethylphosphine, tricyclopentyl (or hexyl) phosphine, diphenylbutyl phosphine, diphenylbenzylphosphine, triphenylphosphine, dimethylphenyl phosphine, methyl diphenyl phosphine. , dimethyl propyl fssfina, the tritolylphosphines and the corresponding arsines and stibines. Including as bidentate ligands are of the type - tetramethyl difosfinoetano, difosfinopropano tetramethyl, tetraethyl difosfinoetano, difosfinopropano tetrabutyl difosfinoetano diethyl sulfoxide, tetraphenyl difosfinoetano, difosfinoetano tetraperfluorofenil, difosfinobutano tetraphenylborate, diphenyl difosfinaetano dimethyl, diethyl and diphenyl propane tetratrolil difosfinoetano diphosphine.

Examples of other suitable ligands are phosphabicyclohydrocarbons, such as 9-hydrocarbyl-9-phosphabicyclononane wherein the smaller P containing ring contains at least 5 carbon atoms. Some examples include 9-aryl-9-phosphabicyclo (4.2.1) nonane, (di) alkyl-9-aryl-9-phosphabicyclo (4.2.1) nonane, 9-cycloalkenyl-9-phosphabicyclo- (4.2.1) nonane , and Sus (3.3.1) and (3.2.1) counterparts, as well as triennial counterparts.

The branched primary alcohol composition of the invention is suitable for the manufacture of anionic, nonionic, and cathodic reagents, preferably the two forcing agents, more preferably the anionic. Specifically, the primary branched alcohol composition of the invention can be used as a precursor for the manufacture of anionic sulfates, including alcohol sulfates and oxy-alkylate alcohol sulfates, including alcohol sulfates, and nonionic oxyalkylate sulfates.

Any known technique can be used here to sulfate alcohols. The composition of • primary alcohol can be directly sulfated, or first oxyalkylated followed by sulfation. A preferred class of compositions comprises at least one anionic reagent comprising the condensation product of C8 to C36, particularly the branched primary alcohol composition Cu to C19 • with or without ethylene oxide and / or propylene oxide, wherein the number of ethoxy groups is in the range from 3 to 12 and the ethoxy / propoxy ratio is from 4 to 12, followed by sulfation.

The general class of anionic reagents or alcohol ethoxy sulphates can be characterized by the chemical formula: where R represents the hydrophobic radical of branched olefin, x represents the average number of oxyethylene groups per molecule and is in the range from 0 to 12, and M is a cation selected from an alkali metal ion, an ammonium ion, and mixtures of these. Of course, the reactant may be oxyalkylated with any oxirane containing another compound, in admixture with, or sequentially with, ethylene oxide.

The sulfonation processes are described, for example, in US Patent Nos. 3,462,525, published on August 19, 1969 by Levisnky et al., 3,428,654, published on February 18, 1969 by Rubinfeld et al., 3,420,875 published on January 7, 1969 by Disalvo et al., 3,506,580 published on April 14, 1970 by Rubinfeld et al., 3,579,537 published on May 18 , 1971 by Rubinfeld et al., And 3,524,864 published on August 18, 1971 by Rubinfeld et al. Suitable sulfation processes include sulfation with sulfur trioxide (S03), sulfation with chlorofulphonic acid (C1S03H) sulphation with sulfamic acid (NH2S03H). When concentrated sulfuric acid is used to sulfate alcohols, the concentrated sulfuric acid is typically from 75 to 100, preferably from 85 to 98 weight percent, in water. Suitable amounts of sulfuric acid are generally in the range from 0.3 to 1.3, preferably from 0.4 to 1.0 moles of sulfuric acid per mole of alcohol.

A typical sulfur trioxide sulfating process includes contacting liquid alcohol or its ethoxylate and gaseous sulfur trioxide at atmospheric pressure in the reaction zone of a water-cooled down-film desiccant at temperature in the range from 25 ° C to 70 ° C to produce the sulfuric acid ester of the alcohol or its ethoxylate when it leaves the falling film column and is neutralized with alkali metal solution, for example, sodium or potassium hydroxide, to form the sulfate salt of the alcohol or the alcohol salt of ethoxysulfate.

Suitable oxyalkylated alcohols can be prepared by adding the alcohol or mixture of alcohols of a calculated amount which will be oxyalkylated, for example, from 0.1 to 0.6, preferably from 0.1 to 0.4 percent by weight, based on the total alcohol, of a strong base , typically an alkali metal or hydroxide of an alkaline earth metal such as sodium hydroxide or potassium hydroxide, which serves as a catalyst for oxyalkylation. The resulting mixture is dried, while removing the vapor phase. any water present, and an amount of alkylene oxide calculated to provide from about 1 mole to about 12 moles of alkylene oxide per mole of alcohol is then introduced and the resulting mixture is allowed to continue to react until the oxide is consumed. alkylene, the course of the reaction is followed by the decrease in reaction pressure.

Oxyalkylation is typically carried out at elevated temperatures and pressures. The range of suitable temperatures is from 120 ° C to 220 ° C. With the preferred range from 140 ° C to 160 ° C. A suitable reaction pressure is achieved by introducing into the reaction vessel the "required amount of alkylene oxide which has a high vapor pressure at the desired reaction temperature." As a consideration of process safety, the partial pressure of the alkylene oxide reagent is 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, at a concentration of the vapor phase of approximately 50 percent or less. The reaction, however, can surely be achieved with a higher concentration of alkylene oxide, higher total pressure and higher partial pressure of alkylene oxide if appropriate precautions, known in the art, are taken to handle the risk of explosion. With respect to ethylene oxide, a total pressure of between about 376 and 858 kPa, with a partial pressure of ethylene oxide between 345 and 621 kPa, is particularly preferred, while a partial pressure of between about 50 and 90 psig is considered most preferred is a partial pressure of ethylene oxide between 238 and 445 kPa. The pressure serves as a measure of the degree of reaction and the reaction is considered to be substantially complete when the pressure does not decrease much with it. weather .

It should be understood that the oxyalkylation process serves to introduce a desired number of alkylene oxide units per mole of alcohol oxyalkylate. For example, the treatment of a mixture of alcohols with 3 moles of ethylene oxide per mole of alcohol serves to affect the ethoxylation of each alcohol molecule with an average of 3 ethylene oxide radicals per mole of alcohol radicals, although one Substantial proportions of alcohol radicals will be combined with more than 3 ethylene oxide radicals and an approximately equal ratio will be combined with less than 3. In a typical mixture of the ethoxylation product, there is also a lower proportion of unreacted alcohol.

Other alkylene oxides, such as propylene oxide and butylene oxide, can be used. These can be added as a heterogeneous mixture to the alcohol or sequentially to make a block structure.

The composition of the sulfated primary alcohol of the invention can be used as a reagent in a wide variety of applications, including detergents such as granular laundry detergents, liquid laundry detergents, liquid dishwashing detergents; and miscellaneous formulations such as general purpose cleaning agents, liquid soaps, shampoos and liquid scouring agents.

The sulfated primary alcohol composition of the invention finds particular use in detergents, specifically laundry detergents. These are generally comprised of several compounds, in addition to the sulphated primary alcohol composition of the invention: other reactants of the ionic, nonionic, amphoteric or cationic type, enhancing agents (phosphates, zeolites), enhancing coagents (polycarboxylates), bleaching agents and their activators, foam control agents, enzymes, anti-grit agents, optical brighteners, and stabilizers.

Liquid laundry detergents comprise the same compounds as granular laundry detergents, but generally contain less of the inorganic compound of the enhancing agent. Hydrotropes are frequently present in liquid formulations of detergents. The general purpose cleaning agents may comprise other reagents, enhancing agents, hydrotropes and alcohol solubilizers.

In addition, for reagents, the cleaning and washing agents may contain a large amount of the salts of the enhancing agent in amounts up to 90% by weight, preferably between 5-35% by weight, to intensify the cleaning action. Examples of common inorganic enhancing agents are phosphates, polyphosphates, alkali metal carbonates, silicates and sulphates. Examples of organic enhancing agents are polycarboxylates, aminocarboxylates, such as ethylenediaminetetraacetate, nitrilotriacetates, hydroxycarboxylates, citrates, succinates and substituted or unsubstituted alkanedi and polycarboxylic acids. Another type of enhancing agent, useful in liquid laundry and granular laundry agents, includes different water-insoluble materials which are capable of reducing the hardness of water, for example, by the ion exchange process. In particular sodium complex aluminosilicates, known as type A zeolites, are widely useful for this purpose.

The formulations may contain percompounds with a bleaching action, such as perborates, percarbonates, persulfates and peroxy organic acids. The formulations containing the percompounds may contain stabilizing agents, such as magnesium silicate, sodium ethylenediaminetetraacetate or sodium salts of phosphonic acid. In addition, bleaches activators can be used to increase the efficiency of inorganic persalts at low wash temperatures. Particularly useful for this purpose are substituted carboxylic acid amides, for example, tetraacetylethylenediamine. , substituted carboxylic acids, for example, isonoyloxybenzenesulfonate and sodium cyanamide.

Examples of suitable hydrotropic substances are alkali metal salts of benzene, toluene, and xylene sulfonic acid; alkali metal salts of formic, citric, and succinic acid, alkali metal chlorides, urea, mono-, di-, and triethanolamine.

Examples of solubilizers of alcohols are ethanol, isopropanol, mono- or polyethylene glycols, monopropylene glycol and ether alcohols.

Examples of foam control agents are high molecular weight fatty acid soaps, paraffinic hydrocarbons, and silicone-containing defoamers. In particular, hydrophobic silica particles are efficient agents for the control of foam in these laundry detergent formulations.

Examples of known enzymes that are affective in laundry detergent agents are protease, amylase and lipase. Preferably the enzymes that have their optimal development are given to the design conditions of the cleaning and washing agent.

A large number of fluorescent whitening agents are described in the literature. Laundry laundries, disulfonate derivatives of diaminostilbene and substituted distiribibiphenyl are particularly suitable.

As agents for preventing grayish darkening, water-soluble colloids are preferably organic natural. Examples are water-soluble polyanionic polymers such as polymers and copolymers of acrylic and maleic acid, cellulose derivatives such as carboxymethyl cellulose methyl and hydroxyethyl cellulose.

In addition, of one or more of the above-mentioned reagents and other compounds of the detergent composition, the compositions according to the invention typically comprise one or more inert compounds. For example, the balance of the liquid detergent composition is typically an inert solvent or diluent, most commonly • water. Powdered or granular detergent compositions typically contain amounts of inert filler or transport materials.

The following examples will illustrate the nature of the invention.

Example 1 These examples demonstrated the manufacture of a skeletally islated C? 6 olefin, subsequently converted to a skeletonically isomerized C17 primary alcohol composition according to the invention.

First, 1 liter of define NEODENE 16, a C α 6 linear α-olefin commercially available from Shell Chemical Company, was dried and purified through alumina. The olefin was then passed through a tube-shaped oven at about 250 ° C fixed with a feed rate of about 1.0 ml / minute and using a nitrogen flow of about 91 ml / minute. Working from the top of the tube-shaped furnace, it was charged with fiberglass, then 10 ml of silicon carbide, then the catalyst, followed by 5 ml of silicon carbide, and more. Glass fiber in the bottom. The volume of the tube-shaped oven was 66 ml. The tube-shaped furnace reactor has three temperature zones, with a multiple thermocouple inserted in the tubular reactor and positioned such that the upper, lower temperature and at three different places in the catalyst can be monitored. The reactor is inverted and installed in the furnace. All three zones, including the catalyst zone, were maintained in the reactor at 114 kPa.

The amount of catalyst used was 23.1 g, or 53 ml in volume. The type of catalyst used to structurally isomerize the NEODENE 16 olefin was a 1.59 mm extrudate and H-ferrierite containing 100 ppm of metallic palladium was calcined.

This catalyst was prepared according to Example C of USP 5,510,306, reproduced in part here for convenience. An ammonium ferrierite having a molar ratio of silica to alumina of 62: 1 was used as an initial zeolite, a surface area of 369 square meters per gram (P / Po = 0.03), a soda content of 480 ppm and -hexane with sorption capacity of 7.3 g per 100 g of zeolite. The catalyst compound was mixed using the Lancaster mixer. The mixed catalyst material was extruded using a Bonnot 25.4 mm or 57.2 mm cube extruder.

The catalyst was prepared using 1% by weight acetic acid and 1% by weight citric acid. The Lancaster mixer was charged with 645 grams of ammonium ferrierite (5.4% loss in ignition) and 91 grams of CATAPAL D alumina (LOI of 25.7%). The alumina was mixed with the ferrierite for 5 minutes during this time 152 milliliters of deionized water were added. A mixture of 6.8 grams of glacial acetic acid, 7.0 grams of citric acid and 152 milliliters of deionized water was added slowly to the mixer in order to peptize the alumina. The mixture was mixed for 10 minutes. 0.20 grams of tetraamine palladium nitrate in 153 grams of deionized water was then added slowly while the mixture was mixed for a further 5 minutes. Ten grams of METHOCEL F4M hydroxypropylmethylcellulose were added and the zeolite / alumina mixture was transferred to the. Bonnot extruder of 2.25 inches and was extruded using a flat die with holes of 1.59 mm.

The wet extrudates were then dried in a heating oven at 150 ° C for 2 hours, and then decreased to 175 ° C for 4 hours.

After drying, the extrudates were calcined in an air flow at 500 ° C for two hours.

The olefin was passed through a reactor in the form of a 5 hour period oven. Samples of 36.99 g and 185.38 g were collected in approximately 1 and 5 hours, and combined for a total of approximately 222 g. A portion of this sample was then vacuum distilled at 0.533 kPa to obtain a predominant amount of the C? 6 olefin skeletonically isomerized by collecting the distillate cuts with boiling points of 160 ° C at the bottom point and 85 DC at the head , and 182 ° C in the bottom and 75 ° C in the head.

A 90 gram sample of the 110.93 grams of the skeletally isomerized olefin was then hydroformylated using the modified oxo process. The 90 grams of the skeletally isomerized olefin reacted with hydrogen and carbon monoxide in a molar ratio of about 1.7: 1 in the presence of the phosphine modified cobalt catalyst at a temperature of up to 185 ° C and a pressure of about 7684 kPa per four. hours and a half in a 300 cc nitrogen purged autoclave. After the reaction was completed, the product was cooled to 60 ° C. 40 grams of the hydroformylated product were drained into a 100 ml flask and distilled under vacuum for 4 hours at 0.533 kPa with increments of temperature from the start of 89 ° C to the final temperature of 165 ° C. The distillate cuts of 20.14 g and 4.12 g were taken at 15-5 ° C and 165 ° C, respectively, and combined in a 100 ml flask. 0.2 g of sodium borohydride was added to the distillate sections in the flask, stirred, and heated to 90 ° C for a period of 8 hours to deactivate the hydroformylation catalyst and stabilize the alcohols. The distilled alcohol was washed with water at 90 ° C three times, dried with sodium sulfate, and filtered into a 100 ml flask. The alcohol was then vacuum distilled for one hour to distill the remaining water. The product was then subjected to NMR analysis and sulfation to test the solubility in cold water, detergency and biodegradability.

Example 2 This example will demonstrate the manufacture of a skeletonically isomerized C13-14 olefin, subsequently converted to skeletonically isomerized C? 4-i5 primary alcohol according to the invention.

A C13-14 linear internal olefin having a composition of 53.38% linear CX3 olefin, 45.24% linear C 4 4 olefin, 0.96% branched C13 olefin, and 0.29% branched Cu olefin, was subjected to skeletal isomerization. Same procedure and type of equipment as described in example 1. The defina was passed through the tubular furnace for 26 hours, except that after 8 hours the tube temperature was increased in all three zones to 275 ° C, Samples were collected at 13 hours, 18 hours, 20 hours and 26 hours, samples of the skeletally isomerized olefins and were combined for a total of 774 g.

Gaseous and liquid products were collected after 4.5 hours (at 250 ° C) and 15.5 hours (at 275 ° C) were analyzed in the stream in order to determine their composition. Its feed was converted to 250 ° C, 70.1% of C13 olefin, and its feed of 75.6% of the C? 4 olefin was converted. At these conversion levels, the selectivity of branched olefins C? 3 and C14 was 96.3% and 97.8%, respectively. 67.4% of the C? 3 olefin feed was recovered as skeletally isomerized C? 3 branched olefin. 74.0% of the C? 4 olefin feed was recovered as skeletally isomerized Cu branched olefin.

The feed of C? 3 olefin became 79.4%, the C? 4 olefin feed became 82.2% at 275? C. at these conversion levels, the selectivity of branched olefins C3 and Ci4 was 91.5% and 92.1%, respectively. 72.6% of the skeletally isomerized C? 3 branched olefin feed was recovered. 75.6% of the skeletally isomerized branched olefin Ci4 feed was recovered.

The skeletally isomerized olefin was then vacuum distilled at 0.533 kPa. 636 grams of boiling distillate were collected in the bottom with a temperature range of 135 ° C to 145 ° C and the head within the range of 108 ° C to 138 ° C. 606 grams of the skeletally isomerized distilled olefin were hydroformylated with the above procedure, except in a 3,785 liter autoclave using the% mol ratio of 37/63 carbon monoxide with hydrogen for a period of 12-13 hours at 4826 to 5516 kPa and 175 ° C. 693 grams of alcohol were collected.

The alcohol was then distilled by instantaneous separation at 0.533 kPa to collect the Ca4-i5 alcohol, with approximately 650 g of the distillate cut at boiling point of 185 ° C and the head at 140 ° C. This cut was treated with 5.0 g of sodium borohydride, heated to about 100 ° C, and then treated with an additional 5.0 grams of sodium borohydride, for a total time of 9 hours hot. The alcohol was washed with water at 90 ° C three times, dried with sodium sulfate, filtered, and distilled under vacuum at 0.533 kPa. The distillate cuts were collected by boiling from 128 ° C to 142 ° C in the head and cold water solubility, detergency and biodegradability tests were carried out.

Example 3 The same procedure that was used in Example 1 to skeletally isomerize a commercially available NEODENE 14 olefin by Shell Chemical Company, which is a C14 α-olefin, with the subsequent conversion to a skeletonically isomerized C15 primary alcohol composition. The tubular furnace was maintained at 250 ° C. The cut of the skeletally isomerized distillate was boiled at 133 ° C in the bottom and 64 ° C in the head and hydroformylated at 8963-9653 kPa for 5 hours with a molar ratio of H2 / C0 of 1.7: 1, using the equipment of example 1.

Example 4 The same procedure as in Example 1 was used to skeletally isolate a NEODENE 12 olefin, a C12 α-olefin, which was subsequently converted to an isomerized primary alcohol composition Ci3. The skeletally isomerized olefin was distilled under vacuum at 2665 kPa, and the distillate cut was collected boiling at 172 ° C in the bottom and 105 ° C in the head and hydroformylated to an alcohol. The hydroformylation equipment was the one used in Example 2 at 2032 kPa during a period of 8 hours, using a ratio of 37/63 mol% of the CO / H gas mixture. The alcohol that was distilled under vacuum at 1333 kPa was collected, with these boiling cuts at 141-152 ° C in the bottom and 127-132 ° C in the head.

Example 5 The same procedure was repeated, the same olefin and the type of equipment used in example 2. The internal olefin C? 3-? 4 was isomerised at 250 ° C. The isomerized olefin that was distilled under vacuum at 0.533 kPa was collected, with these boiling cuts at 95 ° C and 77 ° C at the head, as well as with these boiling cuts between 120 ° C and 175 ° C at the boiling point. bottom and 73 ° C and 106 ° C in the head that was collected under 2665 kPa. The hydroformylation was carried out in an autoclave for 9 hours at a pressure of 8032 kPa using a CO to H ratio of 37/63 mol%. However, the distillate cuts were boiled at 173 ° C in the bottom and 125 ° C in the head and collected and treated with sodium borohydride as in example 2.

Example 6 Each of the primary alcohol compositions described in Examples 1-6 was sulphated by adding chlorosulfonic acid to the primary alcohol composition in drop form. Specifically, the primary alcohol composition was sprayed for 2-3 hours with nitrogen in a flask, after which about 1 ml of methylene chloride per gram of the primary alcohol composition was added. Chlorosulphonic acid was added in the form of drops to the primary alcohol composition in the flask for approximately 25 minutes, while maintaining the temperature at approximately 30-35 ° C. More ethylene chloride was added if the solution became viscous. The solution was then sprayed with nitrogen for 2-3 minutes to facilitate the removal of HCl, after which it was added slowly to a solution of 3A alcohol in cold 50% sodium hydroxide to neutralize the primary alcohol composition. If the pH was less than 8, more than the basic solution was added, until the pH was adjusted between 8-9. If it was very acidic, 50% H2SO4 was added in solution to adjust the pH. The solution was stirred for another hour, and the pH was adjusted according to the established range. The methylene chloride was removed with a rotary evaporator under reduced pressure at approximately 40 ° C under a nitrogen spray.

The primary alcohol compositions were subsequently tested in amount, type, and branching location using the JSME NMR method described herein. For the determination of quaternary carbon atoms, the JSME RMN single cuat technique was used. These results were reported in Table 1 below. Samples of sulphated primary alcohol were also tested for their biodegradability, the results of these are reported in Table II; and the detergency, the results of these are reported in Table III. The examples reported in the tables were arranged in order of chain length for easy viewing, and identified as 6-indicates the sulfate of the corresponding example number. Each of these tests were developed according to the specific procedures above. As a comparison of the example, the branching, biodegradability and detergency of the NEODOL 45 sulphate were tested.

NEODOL 45-S was used as the comparison because this is the current primary alcohol composition commercially available, it was currently used in detergents and is known for its easy biodegradability.

Table I Structural Characterization of MRI (continued) Table 1 Structural Characterization of MRI The above results indicate that the skeletally isomerized branched alcohols according to the invention have a very high average number of branches per molecular chain, exceed 0.7, while the commercial NEODOL 45 has an average number of branches which are smaller, in order of 0.3. The branching patterns are remarkably similar for the different alcohols according to the invention except that the C? 7 branching is curiously deficient in isopropyl termination. The results also indicate an increase in the form in the number of branches attached at the C3 position compared to the absence of any branching at the C3 position of the NEODOL 45 alcohol. Of the types of branches detected, most of the branches are methyl groups for both the alcohols isletically isomerized and the alcohol NEODOL. However, the methyl branches in the skeletally isomerized alcohol are not concentrated in the C2 position, as in the case of NEODOL 45 and other alcohols of conventional detergent range. Another distinguishing characteristic of the skeletally isomerized alcohols is that they contain a greater proportion of branches of the ethyl type than NEODOL 45. In addition, except for the branched alcohol C? 7, most of the modalities were skeletally isomerized in the terminal part of the hydrophobe , as indicated by the high percentage of terminal isopropyl formation, in contrast to none found in NOEDOL 45.

The results also support a conclusion that a predominant number of branches in the skeletally isomerized alcohols are concentrated towards the ends of the molecular chain, for example, in C2, C3, and in the isopropyl terminal position, instead of towards the center of the molecular chain. The NMR data shows a high percentage of branching of methyl, ethyl, and isopropyl for a compound where the branching is predominantly towards the center of the chain, eg, into fourth carbon or any end of the chain, typically having Very low branching percentages at positions C2 and C3. The above data, however, both show a high percentage of branches of methyl, ethyl, and isopropyl as well as a greater amount of branches attached at the C2 position, and C3 at the ends of the carbon chain than the number of branches found in positions C4 or greater of both ends of the molecule that proceeding internally towards the center.

Finally, even though a large number of branches per molecular chain, no quaternary carbon was detected by the modified JSME NMR method. This would suggest that these compounds should easily biodegrade.

Table II % Biodegradation of alcohol sulphates skeletonically isomerized The EOCD 301D biodegradation results indicate that each of the sulphated primary alcohol compositions of the invention are readily biodegradable. Some of the primary alcohol compositions of the invention still exhibit 100% biodegradability at 28 days.

Table III Multisebum detergents of skeletally isomerized alcohols sulfates LSD95 (Less Significant Difference at 95% probability) is 5.0 at both temperatures.

The detergency results indicate that the alcohol sulfate compositions of the invention exhibit extremely good detergency in cold water. For example, 6-2 not so far from the development of sulfated NEODOL alcohol, each with the same length of chains, in both detergents in cold water and hot water. A composition that has good detergency in cold water is one in which superior detergency in cold water over a sulfated NEODOL alcohol of the same chain length. Preferably, however, it is these sulfates of alcohols which have a cold water detergency of 22% greater, more preferably 28% or more.

Example 7 This example demonstrates the manufacture of a mono-branched C12-15 alcohol dimerized from internal olefins using the nickel chelate catalyst.

A flask was charged with 2286.7 grams of a composition of internal C6-C8 definitions containing some olefins with 4, 5, 9 and 10 carbons, and distilled using an 11-plate Oldershaw distillation column with a tank separator condenser with reflux, a trap cooled with dry ice, and a layer of nitrogen. After 37 hours of distillation, these cuts were collected that distilled to 138 ° C in the bottom and 125 ° C in the head to give a total number of approximately 1200 grams. These cuts represent the last light ones of the olefin, C-8.

The 1200 grams of the C4-8 olefin feed were dimerized by the following method. The 1200 grams of the olefin were drained in a 5 liter round bottom flask equipped with a condenser, a condenser with dry ice, a thermocouple, a water bath, and a nitrogen blanket. 19.74 grams of nickel hexafluoroacetoacetyl acetonate (nickel catalyst) and 53.76 g of a solution of 11/89% by weight of diethylaluminum ethoxide in cyclohexane (aluminum solution) were added sequentially and stirred in the olefin. The reaction mixture was heated to 35 ° C for 6.5 hours, then an additional 14.38 grams of the aluminum solution was added, heated to 37 ° C for an additional 2 hours., then an additional 4.0 grams of the nickel catalyst and 13.75 g of the aluminum solution were added, it was heated from 35 ° C to 37 ° C for another 10 hours, then an additional 15.55 grams of the aluminum solution was added followed by heating by another 4 hours, then 14.4 grams of the aluminum solution was added, followed by heating for another 5 hours, then 21.0 grams of the aluminum solution and 5.0 grams of the nickel catalyst were added, followed by heating for another 3 hours. , then 4.18 grams of the nickel catalyst and 20.1 grams of the aluminum solution were added.

Subsequently, the product of the reaction in the flask was cooled with 100 g of citric acid and 22 g of a sodium bicarbonate solution per 0.946 liters (quart) of water, and filtered.

The dimerized C4-8 olefin was then subjected to another distillation to obtain cuts having predominantly C13-3.4 olefins. The distillation was carried out as above, except that it was done with a 10-dish Oddershaw column, and these cuts distilled from 169 ° C to 194 ° C in the bottom and from 129 ° C to 155 ° C in the head, to give a total of 188.5 grams.

Then 150 grams of this batch was subjected to hydroformylation in a 500 ml autoclave, using the modified Oxo process. 150 grams of the dimerized define were reacted with hydrogen and carbon monoxide in an H2 / C0 ratio of 2, in the presence of phosphine modified cobalt catalyst and potassium hydroxide in ethanol at a temperature of up to 180 ° C, a stirring speed of 1250 rpm, and a pressure of 6894 kPa, for 20 hours. After the reaction was completed, the product was cooled to 60 ° C.

The hydroformylated dimerized alcohols were subjected to another instantaneous volatilization by removing any olefins and unconverted paraffins. These cuts were collected that distilled from 182 ° C to 250 ° C in the bottom and from 99 ° C to 112 ° C in the head, were neutralized with sodium borohydride. The distilled cuts, in total 300 ml, were added to a round-bottomed flask, stirred and heated to 50 ° C, where 0.6 grams of sodium borohydride was added and left to react for about 2 hours, then added. 0.6 grams of sodium borohydride and left reacting for another 1.5 hours a. 75-80 ° C, and then reacted for another 2 hours at 98-100 ° C. The solution was allowed to cool, transferred to a 500 ml flask, washed by rinsing with deionized water at 70 ° C under aeration, allowed to stand, 20 ml of ethyl ether was added, stirred, and separated. The aqueous phase was drained and the process repeated two more times using ethyl ether. After they were washed, 10 grams of sodium sulfate was added to the alcohol, stirred and allowed to stand. The product was filtered, the liquid was transferred to a 250 ml flask, and then subjected to another distillation to release the solution from the light ones. The obtained distillates were discharged up to 102 ° C in the bottom and 163 ° C in the head, and 82.91 ml of the bottom content were recovered. These contents were mono-branched C12-16 alcohols, having alcohols of 42% C14, 44% C15 and 8% C6 as determined by GCMS, and subjected to analytical testing and another reaction to make the sulfates.

Example 8 These examples demonstrate the preparation of a C13-17 dimerized monobranched alcohol from defines using a nickel carboxylate catalyst.

The same procedure was followed as used in Example 1 above with the following exceptions. The amount of distilled internal C4-10 olefins was 2427.7 grams. The 712.5 grams of distillate that was boiling from 120 ° C to 154 ° C in the bottom and 89 ° C to 129 ° C in the head were collected. The reflux was maintained in 5 seconds, and 7 seconds for the exit. The distillate cuts were predominantly internal olefins of C6-9 carbon chains. The 702.6 grams of these olefins were dispersed in a 2 liter flask using 0.493 g of nickel 2-ethylhexanoate-thi flluoroacetate in 5 ml of cyclohexane and 12 ml of a 1 molar solution of ethyl aluminum dichloride in hexane, (first batch of catalyst) while injecting the dimerization catalysts into the olefins. The contents of the flask were heated at 35-38 ° C on average during the course of the reaction. After approximately 3 hours of heating, a second batch of catalyst was added with the same amount. After another hour of heating, a third batch of catalyst was added with the same amount, and after 1 hour and 15 minutes, it was added. a fourth batch of catalyst with the same amount. After 6. 5 hours, a fifth batch of catalyst was added with the same amount, and after 7 hours of heating, another batch of catalyst was added with the same amount, and finally after another 1.5 hours the final batch of catalyst was added with the same amount. The contents of the flask were heated for another hour.

To neutralize the dimerization catalyst, 22 g of sodium bicarbonate in 250 g of deionized water were added to 100 g of citric acid in 100 grams of deionized water, where more water was added to make a 1 liter batch. The dimerized olefins were emptied into a funnel with liter of a citric acid / bicarbonate solution, stirred, vented, separated, and repeated. The neutralized dimerized solution was dried with sodium sulfate as mentioned above.

As in Example 1, the olefins were again distilled to acquire Ce-g olefins.

These distillate cuts were collected that boiled at 157 ° C in the bottom and 125 ° C in the head at 5.5 kPa, and boiled from 139 ° C to 164 ° C in the bottom at 1866 kPa and 179 ° C to 240 ° C in the bottom at 1.9 kPa, for a total of 231.95 grams of distillate.

The dimerized distillate was hydroformyl as described above and distilled by instantaneous separation at about 0.5-0.7 kPa. 1.39 grams of sodium borohydride was added to 211.48 g of the distilled alcohol, heated to 50 ° C for 1 hour, after which another 1.3 g of sodium borohydride was added and heated at 90 ° C for four hours and cooled .

The product was washed as above, and distilled again with those sections of the distillate which boiled at 141.5 to 240 ° C in the bottom and 100 ° C at 104 ° C in the head which was collected at 0.4 kPa. Mono-branched C13-17 alcohols, having alcohols of 25% C14, 40% C15, and 25% C? 6 as determined by GCMS, and subjected to analytical testing and another reaction to make the sulfates.

Example 9 This example demonstrates the preparation of C13 dimerized monohydric alcohols, 15.17 from alpha olefins.

In this example, a mixture of 600 g of NEODENE 6 α-olefin, a C6 olefin and 800 g of NEODENE 8 of α-olefin, a C8 olefin, containing 5.32 g of ethylaluminum dichloride, was added to the 5 liter flask. The same procedure was used as in example 1 followed by the following differences. A solution of 7.9 g of nickel 2-ethylhexanoate-trifluoroacetate in 6.35 g of cyclohexane (the nickel solution) was added and heated. The flask was maintained from 33 ° C to 38 ° C throughout the course of the reaction. 6.7 ml of aluminum solution were prepared as prepared in example 2 and 5 ml of the nickel solution was injected into the reaction flask for about 8 hours of heating. 1.5 liter of neutralizing sodium citrate was used to neutralize the dimerized olefins, separated, and repeated again. The dimerized product was distilled, these boiling distilled cuts were collected from 149 ° C to 160 ° C in the bottom and 137 ° C to 148 ° C in the head, at 8.0 kPa, from 120 ° C to 133 ° C in the bottom and 110 ° C to 122 ° C at the head 1,2 kPa, and from 127 ° C to 149 ° C at the bottom and 118 ° C to 145 ° C at the head at 1.3 kPa, for a total of 786.4 grams of distillate. 730 g of these dimerized olefins were hydroformylated in a 3,785 liter autoclave, reacted at temperatures up to 240 ° C at pressures up to 7894 kPa. 809 g of the hydroformylated olefins were treated with 6.5 g of sodium borohydride, as above, followed by the addition of another 6.5 g of sodium borohydride and heated, and a "third addition of 4.95 g followed by 6 hours of heating. up to 99 ° C.

The hydroformylated olefins treated as in Example 1 were washed, filtered, and distilled with those boiling cuts at 152 ° C at 81 ° C at the bottom and 137 ° C at 172 ° C at the head at 0.8 kPa, for a total of 495 grams of mono-branched alcohols of C13, C? 5 and C? 7. The sample was analytically probed and sulfated as described below.

Example 10 Each of the mono-branched alcohol compositions described in Examples 7-9 was sulphited by adding chlorosulphonic acid in dripped form to the alcohol composition. Specifically, the alcohol compositions were sprayed for 2-3 hours with nitrogen in the flask, after which about 1 ml of methylene chloride per gram of alcohol composition was added. The chlorosulfonic acid was added in dripped form to the alcohol composition in the flask for approximately 25 minutes, while maintaining a temperature of 30-35 ° C. More methylene chloride was added if the solution became viscous. The solution was then sprayed with nitrogen for 2-3 minutes to facilitate the removal of HCl, after which 50% sodium hydroxide was slowly added to a 3A alcohol solution to neutralize the alcohol composition. If the pH was lower than 8, more of the basic solution was added, until the pH was adjusted between 8-9. If it was too acidic, a 50% H2SO4 solution was added to adjust the pH. The solution was added for another hour, and the pH was adjusted according to the established range. The methylene chloride was removed by rotary evaporation under a reduced pressure at 40 ° C under nitrogen spray.

The alcohol compositions of Examples 1-3 were subsequently tested in amount, type and location of the branches using the described JSME NMR method described herein. It was used for the determination of quaternary carbon atoms, the JSME single-NMR technique described here. These results are reported in Table 1 below. • The average carbon number was determined by GCMS. Samples of sulfated primary alcohol were also tested for their biodegradability, the results of these are reported in Table II; and the detergency, the results of these are reported in Table III. The samples reported in the tables are arranged in order of chain length for easy visualization and identified as 6- indicates the sulphate of the corresponding example number. Each of these tests were developed according to the specific procedures above. As a comparison of the example, its branching, biodegradability and detergency of NEODOL 45 sulphate was tested. NEODOL 45-S was used as the comparison because this is the current commercially available primary alcohol composition, which was then sulfated, It is currently used in detergents and is known for its easy biodegradability. Also as a comparison, a sulfated EXXAL 13S alcohol is believed to be subject to biodegradation test to have C? 3 alcohols and derived from propylene oligomerization through acid catalysis and then subjected to hydroformylation using an oxo process. EXXAL 13 was reported to have approximately 3-4 methyl branches per molecule of tridecyl alcohol.

Table IV Structural Characterization of NMR (continued) Table IV Structural Characterization of NMR * approximately 21% of the branches were conjugated with the branches of methyl or adjacent carbons in the chain. ** Includes propyl and butyl branches.

The results indicate that the dimerized alcohols according to the invention look very much the same as the alcohols of NEODOL with respect to the branching positions, according to the NMR analyzes. Specifically, some branches were located at the positions of the C2- • carbons, since the average number of branches - of the dimerized alcohols far exceeded that of the alcohols NEODOL, the center of. The molecular chain of carbons must be where the predominant number of branches is located, for example an excess of 80%. By center it is understood that position C is towards the center of each end of the molecule.

Also notable is the higher percentage of ethyl branches in the dimerized alcohols of the invention compared to the relatively few ethyl branches found in the NEODOL alcohol.

Table V% biodegradation of dimerized alcohol sulphates The OECD 301D biodegradation results indicate that each of the sulfated primary alcohol compositions of the invention biodegrades easily, as did the sulfated alcohol NEODOL. Sulfated EXXAL alcohol only in a little biodegradable.

Table VI Multicebo detergents of dimerized alcohol sulfates LSD95 (Less Significant Difference with 95% probability) in 5.0 at both temperatures.

Detergency evaluations indicate that the dimerized alcohols of the invention have superior or equal detergency in cold water compared to the sulfated alcohol NEODOL.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (25)

1. A branched primary alcohol composition, characterized in that it has 11 to 36 carbon atoms and an average number of branches per molecule of 0.7 to 3.0, said branching comprises methyl and ethyl branches.

2. A branched primary alcohol composition according to claim 1, characterized in that the average number of branches per molecule has a range of 1.0 to 3.0.

3. A branched primary alcohol composition according to claim 1 or 2, characterized in that the average number of branches per molecule has a range of 1.5 to 2.34.

A branched primary alcohol composition according to any one of claims 1 to 3, characterized in that it comprises less than 0.5% of atoms of quaternary carbon atoms.

5. A branched primary alcohol composition according to any one of claims 1 to 4, characterized in that it comprises less than 0.5% linear alcohols.

6. A branched composition according to any of claims 1 to 5, characterized in that at least 40% of the number of branches in the alcohol are methyl branches.

7. A branched alcohol composition according to any of claims 1 to 6, characterized in that from 5% to 30% of the number of branches in the alcohol are ethyl branches.

8. A process for preparing a ramified primary alcohol composition according to claim 1, characterized in that the process comprises the steps of: a) contacting a define feed comprising linear olefins having at least 10 carbon atoms with an effective catalyst to skeletally isomerize said linear olefin to produce a branched olefin of the same number of carbons; Y b) converting said branched olefin to said primary alcohol composition.

9. A process according to claim 8, characterized in that the skeletal isomerization catalyst comprises a molecular sieve having at least one channel with a free crystallographic diameter along the xy / oy planes of view (001) with a range of 0.42. at 0.70 nanometers, the molecular sieve is preferably a zeolite having the typical structure of ferrierite.

10. A process for preparing a branched primary alcohol composition according to claim 1, characterized in that it has from 13 to 21 carbon atoms, this process comprises the steps of: a) dimerizing, in the presence of a dimerization catalyst, an olefin feed comprising a C6-? olefin or to produce a C12-20 branched olefin, "and b) converting said C12-20 branched olefin into said branched primary alcohol composition.

11. A process according to claim 10, characterized in that the olefin feed comprises at least 90% of linear olefins.

12. A process according to claim 10 or 11, characterized in that the olefin feed comprises at least 50% of linear olefins.

13. A process according to any claim 10 to 12, characterized in that said dimerization catalyst comprises a combination of nickel carboxylate with an alkylaluminum halide, or a combination of a nickel chelate with an alkylaluminum alkoxide.

14. A process according to any claim 8 to 13, characterized in that the conversion of the olefin to alcohol in step b) is effected by hydroformylating the olefin with carbon monoxide and hydrogen, in the presence of the hydroformylation catalyst.

15. A branched primary alcohol alkoxylate composition, characterized in that it is prepared by reacting a branched primary alcohol composition according to any of claims 1 to 7 with an oxirane compound.

16. A branched primary alcohol alkoxylate composition according to claim 15, characterized in that the alkoxylate is predominantly ethoxylate, prepared by the reaction of the primary alcohol with ethylene oxide.

17. A branched primary alkyl sulfate, characterized in that it is prepared by sulfating a primary alcohol composition according to any of claims 1 to 7.

18. A branched primary alkyl sulfate, characterized in that it is prepared by alkoxylating and sulfating a primary alcohol composition according to any of claims 1 to 7.

19. A branched primary alkyl carboxylate, characterized in that it is prepared by oxidizing a primary alcohol composition of according to any of claims 1 to 7.

20. A detergent composition, characterized in that it comprises: a) one or more reagents selected from the group of branched primary alcohol alkoxylates according to claim 15, branched primary alkyl sulfates, according to claim 17, branched alkoxylated primary alkyl sulfates according to claim 18; b) an intensifying agent; Y c) optionally one or more additives selected from the group of foam control agents, enzymes, bleaching agents, bleach activators, optical brighteners, enhancing coagents, hydrotropes and stabilizers.

21. A detergent composition according to claim 20, characterized in that the enhancing agent is selected from the group of alkali metal carbonates, silicates, sulfates, polycarboxylates, aminocarboxylates, nitrilotriacetates, hydrocarboxylates, citrates, succinates, substituted alkane-or polycarboxylic acids and unsubstituted, complex aluminosilicates, and mixtures thereof.

22. A detergent composition according to claim 20 or 21, which contains bleaching people selected from the group of perborates, percarbonates, persulfates, peroxy organic acids and mixtures thereof.

23. A detergent composition according to any of claims 20 to 22, characterized in that it contains a bleach activator which is selected from the group of carboxylic acid amides, substituted carboxylic acids, and mixtures thereof.

24. A detergent composition according to any of claims 20 to 23, characterized in that it contains a hydrotrope which is selected from the group of alkali metal salts of aromatic acids, alkylcarboxylic acids, alkali metal chlorides, urea, mono- or polyalkanolanes, and mixtures of these.

25. A detergent composition according to any of claims 20 to 24, characterized in that it is chosen from the group of granular detergents for laundry, liquid detergents for laundry, dishwashing detergents, soaps, shampoos, and detergent for scrubbing. SUMMARY OF THE INVENTION A new branched primary alcohol composition and the sulfates, alkoxylates, alkoxysulfates and carboxylates thereof are provided which exhibit good detergency and biodegradability in cold water. The branched primary alcohol composition has an average number of branches per chain of 0.7 to 3.0, which has at least 8 carbon atoms and which contains both methyl and ethyl branches. The primary alcohol composition may also contain less than 0.5% atom of quaternary carbon atoms and a significant number of ethyl branches, terminal isopropyl branches and branches at the C3 position relative to the hydroxyl carbon. The process for its manufacture is by skeletal isomerization of an olefin feed having at least 7 carbon atoms or by dimerizing a Ce-io olefin followed by conversion to an alcohol, thus by means of hydroformylation, and finally sulfation, alkylation or both to obtain a detergent reagent. Useful skeletal isomerization catalysts include zeolite having at least one channel with free crystallographic diameter along the x and / or planes and the view (001) ranging from 42 to 70 nanometers. Useful dimerization catalysts include a combination of nickel carboxylate with an alkylaluminum halide, or a combination of a nickel chelate with an alkylaluminum alkoxide.