Branched surfactant manufacture

The present invention relates to methods of making detergent surfactants, including those containing branched chain hydrophobic units.

Conventional detergent surfactants include molecules which have a water-solubilizing substituent (hydrophilic group) and an oleophilic substituent (hydrophobic group). Typically, these surfactants. include hydrophilic groups such as carboxylate, sulfate, sulfonate, amine oxide, polyoxyethylene and the like groups attached to an alkyl, alkenyl or alkaryl hydrophobic group usually containing from about 10 to about 20 carbon atoms. Accordingly, the manufacturer of these surfactants must have access to a source of hydrophobic groups to which the desired hydrophilic group can be chemically attached. The oldest source of hydrophobic groups included natural fats and oils which are converted to soap (i.e., hydrophilic carboxylate) by saponification with a base. Coconut oil and palm oil are still used to make soap as well as to make alkyl sulfate (AS) surfactants. Other hydrophobes can be obtained from petrochemicals, including alkyl benzene which is used to make alkyl benzene sulfonate (LAS) surfactants.

It is stated in the literature that certain branched hydrophobes can be used with profit to make detergent surfactants based on alkyl sulfate. See, for example, U.S. Patent 3,480,556 to deWitt et al. on November 25, 1969. However, the beta-branched surfactants disclosed in the '556 patent were determined to be inferior in certain solubility parameters as shown by their Krafft temperatures. It has also been determined that the surfactants whose branching is directed towards the center of the carbon chain of the hydrophobic have

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MA 24136US much lower Krafft temperatures. See Aqueous Phase Behavior of Surfactants, RG Laughlin, Academie Press, NY (1994), page 347. Accordingly, it was then determined that such surfactants are particularly preferred for use under washdown conditions. cool or cold water (for example 20 ° C to 5 ° C).

One of the problems associated with making detergent surfactants having hydrophobic groups with branching at or near the middle of the chain is mango from a readily available source of such hydrophobes. In the present invention there is disclosed a process for manufacturing such branched hydrophobes and converting them to branched surfactants at or near the middle of the chain.

The present invention encompasses a process for preparing branched olefins at or near the middle of the chain (primarily with methyl branching at or near the middle region of the chain). These materials are then used as a basic feedstock providing the hydrophobic portion of the branched chain detergent surfactants.

The process described herein is designed to provide branched reaction products which are predominantly (85% or more) alpha-olefins and which are then converted to hydrophobes by the oxo reaction sequence noted below. Preferably, these branched alpha-olefins contain a total of between about 11 and about 18 (average) carbon atoms and comprise a straight chain whose average length is in the range of 10 to 18. The branching predominantly is monomethyl, but some degree of dimethyl branching and ethyl branching can occur. Advantageously, the process according to the present invention results in low paired branching (1% or less), i.e. little or no quaternary carbon substitution. In addition, there is little

<img file="MA24136A1_D0001.tif" />

MA 24136US contiguous branching (less than about 20%). Of course, a certain amount (about 20%) of the total feedstock used in the subsequent oxo process can remain unbranched. Typically, and preferably from the point of view of cleaning performance and biodegradability, the process according to the present invention provides alphaolefins having: an average number of branches (base of the longest chain) ranging from 0.4 to 2.5; of the branched material, there is essentially no branching on carbons 1, 2 or on the terminal carbon (omega) of the longest chain of the branched material.

After formation and purification of the branched chain alpha-olefin, the feedstock is subjected to an oxo carbonylation process. In this oxo step, a catalyst is used (for example a conventional cobalt carbonyl; see Kirk othmer below) which does not displace the double bond from its initial position. This prevents the formation of vinylidene intermediates (which ultimately give less interesting surfactants) and allows carbonylation to take place at the level of the η ° 1 and n٠ 2 carbon atoms.

Unless otherwise indicated, all percentages, ratios and proportions given herein are by weight. All documents cited in this document are incorporated herein by reference for their relevant part.

As emerges from the foregoing, the present invention therefore encompasses, in a process for preparing hydrophobic precursors of surfactants from hydrocarbon feedstocks by conversion of a carbon-based source or of another hydrocarbon to a mixture of carbon monoxide and hydrogen, followed by the conversion of carbon monoxide and hydrogen to a mixture of straight and branched chain hydrocarbons, the improvement which comprises extracting from said mixture of straight and branched chain hydrocarbons the sub-

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MA 24136US set of branched hydrocarbons of the general formula:

CH₃(CH₂) x — CH (CH₂) y — C = CH₂ ت ٤) in which X is at least equal to approximately 2, y is greater than or equal to 0, and in which the sum of xy is at least equal to approximately 7.

The present invention also encompasses, in a process for preparing hydrophobic precursors of surfactants from feedstocks based on coal or other hydrocarbons by converting these feedstocks into a mixture of carbon monoxide and of hydrogen, followed by the conversion of carbon monoxide and hydrogen into a mixture of straight and branched chain hydrocarbons, the improvement which comprises the extraction from said mixture of straight and branched chain hydrocarbons of the branched hydrocarbon subset of the general formula:

؟ دلا؟ H, H (II)

CH₃(CH₂) p — CH (CH₂) q — CH (CH₂)_r—C = CH₂where P is at least about 2, q is from 1 to 12, r is greater than or equal to 0, and the sum of P, qetr is at least about 6.

The present invention also encompasses, in a process for preparing hydrophobic precursors of surfactants from feedstocks based on coal or other hydrocarbons by converting these feedstocks into a mixture of carbon monoxide and of hydrogen, followed by the conversion of carbon monoxide and hydrogen into a mixture of straight and branched chain hydrocarbons, The improvement which comprises extracting from said mixture of straight and branched chain hydrocarbons a set of branched hydrocarbons comprising a mixture of:

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a) the subset of the monomethyl compounds of the formula:

branching out

ÇH3 H

CH₃(CH₂) x — CH (CH₂) y — C = CH₂ and

b) the subset of the dimethyl compounds of the formula:

ch₃ h

CH₃(CH₂) p — CH (CH₂) q — CH (CH₂ branching) ٢-c = ch₂

The aforementioned branched hydrophobes can then be converted to give the corresponding branched chain detergent surfactants, as set forth below.

Synthesis gas (carbon monoxide / hydrogen) can be produced from feedstocks made from coal or other hydrocarbons such as natural gas and it can be used to form various linear, branched and cyclic, saturated hydrocarbons and insatures, using standard Fischer-Tropsch (FT) chemistry. These processes can be used to produce a range of hydrocarbons meeting the needs of gasoline, diesel and kerosene fuels. The two points relating to the present invention are as follows. First, the recognition that in FT chemistry branching occurs via free radicals and not carbonium ion chemistry. This provides isolated methyl branches without paired dimethyl branches, with few ethyl branches and low levels of contiguous dimethyl branches. Low pressure and low temperature FT chemistry (for example the production of waxes) forms methylenes predominantly in linear form with typically 1 methyl branch for 50 carbon atoms. At higher pressures and / or temperatures (such as those used for gasoline production), 1 methyl branch per 8 carbon atoms can be obtained. The rearrangement to form the

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MA 24136US methyl branch, which occurs contiguously to the catalyst, can be thought of as the shift of a hydrogen atom from beta-methylene to alpha-methylene, effecting its conversion to methyl branch. The catalyst (Fe, Co, Ru, etc.) moves from alpha to beta and, with the insertion of one or more additional methylene (s) between the catalyst and the methine group (ex beta), the isolation of the methyl branch is completed. The second key point is that alpha-olefins can be a major product of FT chemistry.

The present invention takes advantage of these observations to provide a comprehensive method for preparing branched alpha-olefins at or near the middle of the chain which can be converted to obtain the corresponding detergent surfactants, either directly or by formation of intermediate compounds (eg branched chain alcohols) which are then converted to surfactants. Importantly, the surfactants so produced contain little or no contaminants such as paired or contiguous branches or multiple chain branches (i.e. more than about 3 branches). Based on the weight, these contaminants can lower the overall detergent performance and / or the biodegradability of the surfactant products according to the present invention.

The method according to the present invention is generally as follows:

The Fischer-Tropsch process is described in the Kirkothmer Encyclopedia of Chemical Technology, 4th edition, volume 12, pp. 157-164 (1994), edited by Jacqueline I. Kroschwitz, WileyInterscience, NY The oxo process for producing alcohols is described in detail in the Kirk-othmer Encyclopedia of Chemical Technology. 4th edition, volume 1, pp. 903-908 (1991).

1) Synthesis gas, a mixture of carbon monoxide and hydrogen, is typically obtained from

<img file="MA24136A1_D0002.tif" />

MA 24136US of coal or natural gas, but in principle petroleum or other hydrocarbon sources can be used. Air or oxygen is used to partially burn gas, oil, etc. in order to obtain a mixture of carbon monoxide and hydrogen. Similarly, coal or coke can be subjected to the coke / water / qaz reaction to form carbon monoxide and H. The catalytic conversion reaction of carbon monoxide in the presence of water and gas can be used to change the carbon monoxide to hydrogen ratio if necessary. Various standard purification steps are included to remove carbon dioxide, hydrogen sulfide, ammonia, etc.

Gas - + air or ٥2 -&gt; CO H mixture

C + 0 ي CO + H₂ coke / water / gas reaction

CO + HO -&gt; Η₂ + CO₂ (displacement from gas to water)

2) Fischer-Tropsch (FT) chemistry is used to convert synthesis gas into a mixture predominantly composed of hydrocarbons. The conditions can be adjusted to produce a mixture of predominantly linear olefins with a limited number of methyl branches as well as certain cyclic hydrocarbons. Small amounts of other classes of compounds are formed, eg alcohols. Their levels can be somewhat controlled through FT conditions. In any case, it is possible to eliminate them.

CO / H₂ -&gt; Melanqe of synthetic fuels + branched alphaolefins.

3) Distillation and other standard techniques are used to isolate the hydrocarbon fraction of the desired molecular weight containing alpha-olefins. Molecular sieving can be used to separate most of the linear alphaolefins and cyclics from the desired linear methyl branched alpha-olefins. Standard methods using zeolites make it possible to carry out the first mentioned. The treatment with zeolite sieves can be organized in such a way

<img file="MA24136A1_D0003.tif" />

MA 24136US to remove alpha-olefins iso and ante-iso (omega 1) and (omega 2) methyl if desired. Aliphatic hydrocarbons containing 2 paired Me groups or highly branched aliphatic hydrocarbons (including cyclics) can be separated from aliphatic hydrocarbons containing Me groups on different carbon atoms and less branched aliphatic hydrocarbons by selective adsorption of the latter onto a molecular sieve (pore diameter 4.4 to 5.0 Å) and / or pyrolyzed polyvinylidene chloride (Saran) to give gasoline having Improved octane ratings. See Neth Appl. 7111508, 10/25/1971, Chem. Abstracts 76: 88253.

Blend of synthetic fuels ي Branched alpha-olefins

4) Oxo chemistry (CO / Η is used to convert the branched alpha-olefin into the corresponding branched primary alcohol. Any catalyst can be used which makes it possible to obtain alcohols directly or else indirectly by an additional step of hydrogenation of an intermediate aldehyde. However, it is preferable to use catalysts which do not isomerize the double bond of the alpha-olefin prior to carbonylation as is the case when using cobalt / carbon monoxide / organophosphine catalysts in the process. just one step. Conventional cobalt oxo catalysts such as cobalt / carbon monoxide used in the two-stage high pressure process do not isomerize the c = c double bond. The fact that these catalysts can give approximately equal carbonylation at the 1 and 2 carbon positions of the alpha-olefin is fully acceptable. In other words, the mixture produced would be RCHCHCHOH + · RCHHCHOH in which R is a straight fatty chain with limited methyl branching at or near the middle of the chain.

Branched alpha-olefins -&gt; Branched primary alcohols.

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MA 24136US

5) In one aspect of the last step, any standard sulfation technique can be used to convert the above branched alcohol to branched alcohol sulfate. As examples, there may be mentioned sulfur trioxide in a trickle reactor or else sulfur trioxide or chlorosulfonic acid in a batch reactor. In all cases, the acid mixture is quickly neutralized with caustic soda or the like.

Branched Primary Alcohol -&gt; Branched Alkyl Sulfate.

Other surfactants derived from fatty alcohols can also be produced, for example alkyl ethoxysulphates (AES), alkyl polyglycosides (APG), etc. It should be noted that surfactants other than alcohol sulfates or AES can be produced by oxidizing said alcohol or its aldehyde intermediate to give a carboxylate (i.e. a branched chain soap). This soap can in and of itself be an excellent surfactant and / or detergent forming agent. This carboxylate can also be used as a feedstock and converted to acyl taurates, isethionates, sarcosinates, N-methylglucamides or similar surfactants derived from acyl, using methods known in the art.

Branched-chain surfactants of the type obtained by the process according to the present invention can be used in all kinds of cleaning compositions. Such compositions include but are not limited to: laundry detergents in the form of granules, bars and liquids; liquid compositions for washing dishes by hand; personal cleaning products in the form of liquids, gels and bars; shampoos, toothpastes, hard surface cleaners, and the like. Compositions of this type can contain a variety of conventional detergent ingredients. The following list of such ingredients is given for the sake of

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MA 24136US convenience for the formulator and should in no way limit the types of ingredients that can be used with the branched chain surfactants according to the present invention.

The branched chain surfactants according to the present invention can be used in combination with detergent builders. Such adjuvants include, for example, zeolite A from 1 to 10 micrometers, polycarboxylate builders such as citrate, layered silicate builders such as SKS-6 (Hoechst) and phosphate materials, in particular sodium tripolyphosphate (STPP) . Most laundry detergents typically include at least 1% builder, more typically from about 5% to about 80% builder or builder mixtures.

Enzymes such as proteases, amylases, lipases, cellulases, peroxidases and mixtures thereof can be used in detergent compositions containing the branched chain surfactants. Typical detergent compositions contain from about 0.001% to about 5% of commercial enzymes.

The detergent compositions can also contain polymeric soil repellants (SRAs). Such materials include, for example, anionic, cationic and uncharged monomer units, in particular polyester materials. Preferred materials of this type include oligomeric terephthalate esters, oligomers of substantially linear sulfone esters comprising a backbone of repeating terephthaloyl and oxyalkylenoxy units, and sulfonated end moieties derived from phthaloyl. A variety of SRA agents are described, for example, in U.S. Patent Nos. 4,968,451, 4,711,730, 4,721,580, 4,702,857, 4,877,896, 5,415,807 and other references in the literature. These anti-fouling agents typically represent from about 0.01% to about 10% of finished detergent compositions.

Detergent compositions can also

<img file="MA24136A1_D0004.tif" />

MA 24136US optionally contain compositions containing a bleach and one or more bleach activators. When present, bleaches such as percarbonate or perborate (especially ΡΒ1 perborate monohydrate) are typically used at levels of from about 1% to about 30% of the finished detergent compositions. Bleach activators such as nonanoyloxy benzene sulfonate (NOBS) and tetracetyl ethylene diamine (TAED) as well as mixtures of these substances can be used to enhance the bleaching activity of materials such as perborate and percarbonate. When present, the amount of bleach activator is typically from about 0.1% to about 60% of a bleach composition comprising a bleach plus a bleach activator. Other bleaches such as so-called photoactive bleaches (see U.S. Patent No. 4,033,718) can also be used. A particularly preferred photoactive bleaching agent is sulfonated zinc phthalocyanine.

Detergent compositions may also contain clay stain remover / anti-redeposition agents such as ethoxylated tetraethylene pentamine. See US Patent No. 4,597,898. These materials typically represent from about 0.01% to about 10% of fully formulated laundry detergents.

The detergent compositions can also contain from about 0.1% to about 7% of polymeric dispersants which are particularly useful in the presence of zeolite and / or layered silicate builders. Such materials are known in the art (see US Patent No. 3,308,067). Such materials include copolymers based on acrylate and malic acid as described in EP 193,360, as well as polyethylene glycol (PEG).

The deterqentes compositions according to the present invention may also contain various brighteners.

<img file="MA24136A1_D0005.tif" />

MA 24136US optical, agents inhibiting the transfer of dyes (in particular polymers of N-vinylpyrrolidone and N-vinylimidazole), suds suppressors (in particular silicones), chelating agents such as nitrile triacetate, disuccinate ethylene diamine and the like. Such materials typically represent from about 0.5% to about 10% by weight of fully formulated cleaning compositions.

In addition, it will be understood that branched chain surfactants prepared as described in the present invention can be used alone in cleaning compositions or in combination with other detergent surfactants. Typically, fully formulated cleaning compositions contain a blend of types of surfactants to achieve broad spectrum cleaning performance on a variety of soils and stains and under a variety of use conditions. An advantage of the branched chain surfactants according to the present invention is their ability to be easily formulated in combination with other types of known surfactants. Non-limiting examples of additional surfactants which can be used in the present invention at levels typically ranging from about 1% to about 55% include unsaturated sulfates such as oleyl sulfate, 8-alkyl alkoxysulfates. -0 اء (AES, in particular EO 1-7 ethoxysulphates), 8 اء -0 ا alkyl alkoxycarboxylates (in particular EO 1-5 ethoxycarboxylates), 8 اء -0 اء ethers of glycerol, 8 اء -0 alk alkyl polyglycosides and their corresponding sulfate polyglycosides, and α-alpha-sulfone fatty acid esters. Nonionic surfactants such as ethoxylated C 0-8 alcohols and alkylphenols (eg EO (1-10) Cc can also be used. If desired, other conventional surfactants such as betaines and sulfobetaines (sultaines) in 8 اء -2 اء, amine oxides in 8 اء -0 اء and the like can also be incorporated into the compositions.

<img file="MA24136A1_D0006.tif" />

MA 24136US global. One can also use the N-alkylpolyhydroxyamides of fatty acids in 08٠ اء -0 ذ Typical examples include the N-methylglucamides in 8٠ اء -2 اء See WO 9 206 154. Other surfactants derived from sugars include the N-alkoxy-polyhydroxyamides fatty acids such as N- (3-methoxypropyl) glucamide in C 0-8٠اء Glucamides in 08 اح-₂N-propyl to Nhexyl can be used for low foaming. Conventional 20 ء -0 ء soaps can also be used. If high foaming is desired, branched chain C 0-6اء soaps can be used. 4 اء -0 ا alkyl benzene sulfonates (LAS), which are often used in laundry detergent compositions, can also be used with the branched chain surfactants according to the present invention.

The following examples illustrate the use of branched chain surfactants according to the present invention in various cleaning compositions, without however constituting a limitation thereof.

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MA 24136US

EXAMPLE 1

Granular laundry detergents are prepared as follows.

<td></td><td>AT</td><td>B</td><td>VS</td>

<td>Blown powder</td><td></td><td></td><td></td>

<td>Zeolithe A</td><td> 30,0</td><td> 22,0</td><td> 6,0</td>

<td>Sodium sulphate</td><td> 19,0</td><td> 5,0</td><td>م ٦</td>

<td>Polyacrylate</td><td></td><td></td><td></td>

<td>THE ACE</td><td> 13,0</td><td> 11,0</td><td> 21,0</td>

<td>AS * ramifies</td><td> 9,0</td><td> 8,0</td><td> 8,0</td>

<td>Sodium silicate</td><td> —</td><td> 1,0</td><td> 5,0</td>

<td>Soap</td><td> —</td><td> —</td><td> 2,0</td>

<td>Carbonate</td><td> 8,0</td><td> 16,0</td><td> 20,0</td>

<td>sodium</td><td></td><td></td><td></td>

<td>Spray on</td><td></td><td></td><td></td>

<td>ΕΟ7 in 5 ل_4لح</td><td> 1,0</td><td> 1,0</td><td> 1,0</td>

<td>Dry additives</td><td></td><td></td><td></td>

<td>Protease</td><td> 1,0</td><td> 1,0</td><td> 1,0</td>

<td>Lipase</td><td> 0,4</td><td> 0,4</td><td> 0,4</td>

<td>Amylase</td><td> 0,1</td><td> 0,1</td><td> 0,1</td>

<td>Cellulase</td><td> 0,1</td><td> 0,1</td><td> 0,1</td>

<td>NOBS</td><td> —</td><td> 6,1</td><td> 4,5</td>

<td>ΡΒ1</td><td> 1,0</td><td> 5,0</td><td> 6,0</td>

<td>Sodium sulphate</td><td> —</td><td> 6,0</td><td> —</td>

<td>Humidity and miscellaneous</td><td></td><td>Rest</td><td></td>

* Methyl branched cc alkyl sulfate prepared as described above.

A non-aqueous liquid laundry detergent containing a bleach is prepared as follows.

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EXAMPLE II

<td>Component</td><td>% in weight</td><td>Plate (%</td>

<td></td><td></td><td>in weight)</td>

<td>Liquid phase</td><td></td><td></td>

<td>AS * ramifies</td><td> 25,3</td><td>18 to 35</td>

<td>Alcohol ethoxylate Ε05 C12-H</td><td> 13,6</td><td>10 to 20</td>

<td>Hexylene glycol</td><td>Π, 3</td><td>20 to 30</td>

<td>Perfume</td><td> 0,4</td><td>0 to 1.0</td>

<td>Solid</td><td></td><td></td>

<td>Protease enzyme</td><td> 0,4</td><td>0 to 1.0</td>

<td>Anhydrous N citrate</td><td> 4,3</td><td>3 to 6</td>

<td>Sodium perborate (ΡΒ-1)</td><td> 3,4</td><td>2 to ٦</td>

<td>Nonanoylbenzene sulfonate</td><td> 8,0</td><td>2 to 12</td>

<td>sodium (NOBS)</td><td></td><td></td>

<td>Sodium carbonate</td><td> 13,9</td><td>5 to 20</td>

<td>Diethyltriamine acid</td><td> 0,9</td><td>0 to 1.5</td>

<td>pentacetic</td><td></td><td></td>

<td>Optical brightener</td><td> 0,4</td><td>6,٠ to ه</td>

<td>Defoamer</td><td> 0,1</td><td>0 to 0.3</td>

Minor Ingredients ------- Remainder * methyl branched cc alkyl sulfate sodium salt, prepare as described above

A liquid for washing dishes with 1 hand is prepared as follows.

MA 24136US

EXAMPLE III% by weight

Ingredient

Range (%

<td>AS * branched</td><td> 13,0</td><td> 5</td><td>at</td><td> 15</td>

<td>قا_2لح Alkylethoxysulfate</td><td> 15,0</td><td> 10</td><td>at</td><td> 35</td>

<td>ammonium</td><td></td><td></td><td></td><td></td>

<td>Coconut Amine Oxide</td><td> 2,6</td><td> 2</td><td>at</td><td> 5</td>

<td>Betaine ** / Tetr0nic 704 ®</td><td>0.87 to</td><td> 0</td><td>at</td><td> 2</td>

<td></td><td> 0,10</td><td colspan="3">(email.)</td>

<td>Alcohol ethoxylate CgEji</td><td> 5,0</td><td> 2</td><td>at</td><td> 10</td>

<td>Xylene ammonium sulfonate</td><td> 4,0</td><td> 1</td><td>at</td><td> 6</td>

<td>Ethanol</td><td> 4,0</td><td> 0</td><td>at</td><td> ٦</td>

<td>Ammonium citrate</td><td> 0,06</td><td> 0</td><td>at</td><td> 1,0</td>

<td>Magnesium chloride</td><td> 3,3</td><td> 0</td><td>at</td><td> 4,0</td>

<td>Calcium chloride</td><td> 2,5</td><td> 0</td><td>at</td><td> 4,0</td>

<td>Ammonium sulphate</td><td> 0,08</td><td> 0</td><td>at</td><td> 4,0</td>

<td>Hydrogen peroxide</td><td>200 ppm</td><td>0to</td><td colspan="2">300 ppm</td>

<td>Perfume</td><td> 0,18</td><td> 0</td><td>at</td><td> 0,5</td>

<td>Protease Maxatase ®</td><td> 0,50</td><td> 0</td><td>at</td><td> 1,0</td>

Rest

Water and Minor Ingredients * Alkyl sulfate, cc triethanolammonium salt, described above.

Methyl branched, prepared as ** Coconut Alkylbetalin.

Of course, the present invention is not limited to the embodiments described and shown above, from which other embodiments and other embodiments can be provided, without thereby departing from the scope of the invention.