Surfactants are one of many different compounds that make up a detergent. They are added to remove dirt from skin, clothes and household articles particularly in kitchens and bathrooms. They are also used extensively in industry. The term surfactant comes from the words surface active agent.
Link to Sancolo
Figure 1 Surfactants aid the effective washing of dirty rugby kit using low
temperature wash cycles, resulting in environmental benefits.
By kind permission of Stephen Garnett/Wharfedale RUFC.
Surfactants function by breaking down the interface between water and oils and/or dirt. They also hold these oils and dirt in suspension, and so allow their removal. They are able to act in this way because they contain both a hydrophilic (water loving) group, such as an acid anion, (-CO2- or SO3-) and a hydrophobic (water hating) group, such as an alkyl chain. Molecules of water tend to congregate near the former and molecules of the water-insoluble material congregate near the latter (Figure 2).
Soaps were the earliest surfactants and are obtained from fats which are known as glycerides because they are esters formed by the trihydric alcohol, propane-1,2,3-triol (glycerol), with long chain carboxylic acids (fatty acids). The glycerides are hydrolyzed by heating with sodium hydroxide solution to form soaps, the sodium salts of the acids, and propane-1,2,3-triol. The process is known as saponification.
Figure 2 Action of a surfactant.
The glycerides used to make surfactants contain saturated and unsaturated carboxylic acids which have an even number of carbon atoms, generally within the range 12-20, for example, octadecanoic acid (stearic acid), CH3(CH2)16CO2H.
Synthetic surfactants have one very important advantage over soaps. Because soaps form insoluble calcium and magnesium salts with the calcium and magnesium ions in hard water and in the clays which are present in dirt, much of the soap is wasted forming an insoluble scum. However, this is avoided when using a synthetic surfactant. For example, in the anionic surfactants, the carboxylate group in soap is replaced by a sulfonate or sulfate group as the hydrophilic component. The corresponding calcium and magnesium salts are more soluble in water than the calcium and magnesium salts of carboxylic acids.
Surfactants are classified based upon the nature of the hydrophilic "head-groups" as:
In these surfactants the hydrophilic group is negatively charged. They are the most widely used type of surfactants for laundering, dishwashing liquids and shampoos. They are particularly good at keeping the dirt, once dislodged, away from fabrics.
Four anionic surfactants are used:
a) alkylbenzene sulfonates
b) alkyl sulfates
c) alkyl ether sulfates
d) soaps
The most common of the synthetic anionic surfactants are based on the straight chain alkylbenzene sulfonates. Benzene, in slight excess, is mixed with an alkene or chloroalkane in the presence of an acid catalyst, usually a solid zeolite (ion exchange), aluminium chloride (AlCl3) or hydrofluoric acid (HF), to produce an alkylbenzene (sometimes called detergent alkylate).
For example:
The alkylbenzene varies in average molecular mass, depending upon the starting materials and catalyst used and is often a mixture in which the length of the alkyl side chain varies between 10 and 14 carbon atoms. Historically these included branches in the side chains with the result that they biodegrade very slowly and lead to foaming in rivers and sewage plants. By law, in most countries today, the surfactant must have side chains which are not branched so they degrade more rapidly.
The alkylate is sulfonated using an air/sulfur trioxide mixture, and the resulting sulfonic acid is then neutralised with an aqueous solution of sodium hydroxide (often in situ), for example:
Straight chain alkenes for the above process can be produced from ethene using a Ziegler catalyst (triethyl aluminium). Triethyl aluminium reacts with ethene at ca 400 K and 100 atm to form aluminium alkyls, for example:
When heated in excess ethene, straight chain alkenes, with the double bond at the end of the chain (an a-alkene), are produced:
The mixture is then separated into fractions by distillation, the fraction of alkenes containing 10 to 14 carbon atoms being used to make the surfactants.
These are used together with other surfactants in powder and liquid laundry detergents such as Ariel, Daz, Persil and Surf.
Many detergent products, particularly liquids, contain other synthetic anionic surfactants such as alkyl sulfates, esters of linear alcohols (C10-C18) and sulfuric acid. The alkyl sulfates are also used in personal care products such as toothpaste and are manufactured by treating the alcohol with sulfur trioxide. The product is then neutralised with aqueous sodium hydroxide solution to form a sodium alkyl sulfate:
The alcohols are either produced from carboxylic acids obtained from oils, obtained naturally, for example from palm kernel oil or coconut oil, or alternatively from long-chain alkenes, manufactured from ethene.
There are two processes for making the alcohols from ethene. As described above, aluminium triethyl reacts with ethene to produce compounds such as:
where a,b,c are even numbers from 2 to 12. Instead of heating with excess ethene to produce a-alkenes, the aluminium alkyl is treated with oxygen and then water to produce long chain alcohols:
Alternatively, a different process for making the alcohols from ethene is used, known as SHOP (Shell Higher Olefins Process). In the first stage, ethene is passed, under pressure of ca 100 atm, into a solvent (usually a diol, such as butane-1,4-diol) containing a nickel salt at 400 K. It yields a mixture of a-alkenes which are separated by fractional distillation. About 30% are in the range C10-C14.
These are reacted with carbon monoxide and hydrogen (hydroformylation) to yield straight-chain aldehydes, which on reduction form alcohols. For example:
It is possible to convert the other a-alkene fractions (C4-C10 and C14-C40) into the more desirable C10-C14 fraction.
More widely used than simple alkyl sulfates are various types of sodium alkyl ether sulfates (SLES).
In the manfacture of SLES the primary alkyl alcohol (from a synthetic or natural source and typically a blend based around dodecanol) is first ethoxylated with 1 to 3 molar equivalents of epoxyethane (as described below for the manufacture of nonionic surfactants). The product is then sulfated using sulfur trioxide and neutralized with alkali to form the alkyl ether sulfate:
These materials are preferred by product formulators for many applications (dishwashing liquids, shower gels, shampoo, etc) because they are milder to the skin than alkyl sulfates. They also generate less foam which is an advantage in the formulation of laundry machine products.
Soaps are anionic detergents:
With these surfactants, the hydrophilic head is positively charged.
Although they are produced in much smaller quantities than the anionics, there are several types, each used for a specific purpose.
The simplest quaternary system is the ammonium ion:
An alkyl quaternary nitrogen system has alkyl groups attached to the nitrogen atom. An example is:
They are used as fabric softeners with anionic surfactants, helping them to break down the interface between the dirt/stain and the water.
The directly quaternised fatty acid surfactants described above have been replaced for laundry applications by more complicated structures in which there is an ester linkage between the alkyl chains and the quaternary head-group as these are more biodegradable and less toxic. They are known as esterquats.
An example is:
Esterquats give detergents their fabric softening qualities.
These surfactants do not bear an electrical charge and are often used together with anionic surfactants. An advantage is that they do not interact with calcium and magnesium ions in hard water.
They account for nearly 50% of surfactant production (excluding soap). The major group of nonionics are the ethoxylates made by condensing long chain alcohols with epoxyethane (ethylene oxide) to form ethers, for example:
The long-chain alcohol can come from either a synthetic or natural source.
Although they do not contain an ionic group as their hydrophilic component, hydrophilic properties are conferred on them by the presence of a number of oxygen atoms in one part of the molecule which are capable of forming hydrogen bonds with molecules of water.
As the temperature of the surfactant solution is increased the hydrogen bonds gradually break causing the surfactant to come out of solution. This is commonly referred to as the cloud point and is characteristic for each nonionic surfactant. Nonionics are more surface active and better emulsifiers than anionics at similar concentrations. They are less soluble than anionics in hot water and produce less foam. They are also more efficient in removing oily and organic dirt than anionics. Depending on the type of fibre, they can be active in cold solution and so are useful in countries which lack hot water supplies and in developed countries where there is a desire to lower the wash temperatures either to save energy or because of the type of fabric being washed. Nonionics are used in fabric washing detergents (both powders and liquids), in hard surface cleaners and in many industrial processes such as emulsion polymerization and agrochemical formulations.
Amphoteric (or zwitterionic) surfactants are so called because the head-group carries both a negative and positive charge. A range of methods is used to produce such materials, almost all of which contain a quaternary ammonium ion (a cation). The negatively charged group can be carboxylate, -CO2-, sulfate, -OSO3- or sulfonate, -SO3-. One such well-used class is the alkyl betaines which have a carboxyl group. A long-chain carboxylic acid reacts with a diamine to form a tertiary amine. On further reaction with sodium chloroethanoate, a quaternary salt is formed:
Betaines are neutral compounds with a cationic and an anionic group which are not adjacent to one another.
Amphoteric surfactants are very mild and are used in shampoos and other cosmetics. They are said to be pH balanced.
A detergent is made up of many ingredients, some of which are surfactants. An example of the mixture of compounds in a detergent is shown in Table 1.
In this formulation there are seven surfactants, two anionic, three non-ionic and two soaps.
However, there are other ingredients, each with specific functions:
Bulking agents, such as sodium sulfate and water.
Some detergents need anti-caking agents, for example aluminium silicate, which keep the powder dry and free-flowing.
Builders, usually sodium aluminosilicates, a type of zeolite, remove calcium and magnesium ions and prevent the loss of surfactant through scum formation.
Stains can be bleached with oxidizing agents such as sodium perborate (NaBO3.4H2O) and sodium percarbonate (2Na2CO3.3H2O2) which react with hot water to form hydrogen peroxide which in turn reacts with the stain:
However bleach activators are needed for low temperature washes. Sodium perborate and sodium percarbonate do not liberate hydrogen peroxide in cool water. A compound is added to react with them to liberate a peroxycarboxylic acid, RCO3H, which oxidizes stains readily. The most commonly used activator is:
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It is known by its trivial name, TAED, and reacts with the oxidizing agent to form peroxyethanoic acid:
IngredientFunction Sodium silicoaluminate Builder Sodium carbonate Buffering agent Sodium sulfate Bulking agent Sodium carbonate peroxide (sodium percarbonate) Oxidizing agent Sodium
Table 1 Ingredients of a detergent for washing clothes.
Other ingredients which can be added to a detergent include:
Buffering agents - to keep the pH at the appropriate value
Structurants - to give shape to the fabric being washed
Sequestrants - to react with free metal ions which might otherwise cause problems with appearance or scum formation
Optical brighteners - to make the fabrics look brighter and whiter
Antifoaming agents
Enzymes - to remove specific stains: proteases (to remove proteins), amylases (to remove starches), lipases (to remove fats)
Fragrance
Anti-redeposition agents - to prevent dirt being redeposited on fabrics
Skin conditioning agent - to help to keep the skin in good condition
Softness extender - to help keep the clothes 'soft'
Emulsifier - to help keep immiscible liquids as an emulsion
Colorant
Domestic automatic machine laundry liquids are formulated using blends of anionic, nonionic and soap surfactants and various other functional substances. Bleach systems are not compatible with the higher water temperature and cannot be used above ca 315 K.
For hand washing (used for delicate fabrics such as wool or silk), foam-stabilisers are included, to maintain foam. The customer equates the quantity of foam produced with the detergent cleansing action. For the quantity of foam produced the order is:
anionics > soap > nonionics > cationics
The products used in dishwashers are usually powders and contain builders (90-95%), a nonionic surfactant (1-5%), bleach agents with an activator and enzymes. They are formulated with sodium carbonate and sodium silicate to create a very alkaline environment that helps to denature (break down) the fats and proteins left on the used dishes and utensils.
These formulations contain between 13-40% of surfactants which are predominantly alkyl ether sulfates but also include nonionics and amphoterics (betaines).
These tend to be based on alkyl ether sulfates and usually contain small amounts of other surfactants (most typically amphoterics) which help protect the skin from irritation and also condition the hair.
These products are formulated using cationic surfactants (sometimes combined with small amounts of non-ionic surfactants). These are not cleansing products and the cationic surfactant is deposited onto the slightly negatively charged hair or cotton fibre surface, thus giving a lubrication benefit.
In Western Europe all surfactant components of domestic detergents must be biodegradable. This requirement resulted from the fact that the original alkylbenzene sulfonate anionics were based on branched alkenes and these proved resistant to degradation by bacteria at sewage treatment works causing many rivers to suffer from foam. There was also a fear that surfactants could be "recycled" into drinking water. Similar concerns were expressed about nonylphenol ethoxylates and so in the s the industry moved to linear alkylbenzene sulfonates and alcohol ethoxylates as the major ingredients of their formulations. Effective sewage treatment ensures that detergent components which are part of household effluent water are not discharged untreated into rivers and water courses.
The development of compact powders and liquids and refillable packages is designed to reduce packaging waste.
Redesign of washing machines and laundry detergent products (including the addition of bleach activators and enzymes to ensure good stain removal at low temperatures) has resulted in energy savings by reducing water heating and using shorter wash cycles.
Date last amended: 18th March
This is a continuation of PCT International Application Serial No. PCT/US97/, filed Apr. 16, ; which claims priority to Provisional Application Serial No. 60/015,523, filed Apr. 16, .
FIELD OF THE INVENTIONThe present invention relates to processes for manufacturing detersive surfactants, especially those containing branched-chain hydrophobic units.
BACKGROUND OF THE INVENTIONConventional detersive surfactants comprise molecules having a water-solubilizing substituent (hydrophilic group) and an oleophilic substituent (hydrophobic group). Such surfactants typically comprise hydrophilic groups such as carboxylate, sulfate, sulfonate, amine oxide, polyoxyethylene, and the like, attached to an alkyl, alkenyl or alkaryl hydrophobe usually containing from about 10 to about 20 carbon atoms. Accordingly, the manufacturer of such surfactants must have access to a source of hydrophobe groups to which the desired hydrophile can be attached by chemical means. The earliest source of hydrophobe groups comprised the natural fats and oils, which were converted into soaps (i.e., carboxylate hydrophile) by saponification with base. Coconut oil and palm oil are still used to manufacture soap, as well as to manufacture the alkyl sulfate ("AS") class of surfactants. Other hydrophobes are available from petrochemicals, including alkylated benzene which is used to manufacture alkyl benzene sulfonate surfactants ("LAS").
The literature asserts that certain branched hydrophobes can be used to advantage in the manufacture of alkyl sulfate detersive surfactants; see, for example, U.S. Pat. No. 3,480,556 to deWitt, et al., Nov. 25, . However, it has been determined that the beta-branched surfactants described in the '556 patent are inferior with respect to certain solubility parameters, as evidenced by their Krafft temperatures. It has further been determined that surfactants having branching towards the center of carbon chain of the hydrophobe have much lower Krafft temperatures. See: "The Aqueous Phase Behavior of Surfactants", R. G. Laughlin, Academic Press, N.Y. () p. 347. Accordingly, it has now been determined that such surfactants are preferred for use especially under cool or cold water washing conditions (e.g., 20° C.-5° C.).
One problem associated with the manufacture of detersive surfactants having hydrophobe groups with mid- or near-mid chain branching is the lack of a ready source of such hydrophobes. By the present invention, a process is described for manufacturing such branched hydrophobes and converting them into mid- or near-mid chain branched surfactants.
SUMMARY OF THE INVENTIONThe present invention encompasses a process for preparing mid- to near mid-chain branched olefins (primarily, methyl branched at or near the mid-chain region). Such materials are then used as the basic feedstock which provides the hydrophobic portion of branched-chain detersive surfactants.
The process herein is designed to provide branched reaction products which are primarily (85%, or greater) alpha-olefins, and which are then converted into hydrophobes in the Oxo-reaction sequence noted hereinafter. Preferably, such branched alpha-olefins contain from about 11 to about 18 (avg.) total carbon atoms and comprise a linear chain having an average length in the 10-18 region. The branching is predominantly mono-methyl, but some di-methyl and some ethyl branching may occur. Advantageously, the present process results in little (1%, or less) geminal branching, i.e., little, if any, "quaternary" carbon substitution. Moreover, little (less than about 20%) vicinal branching occurs. Of course, some (ca. 20%) of the overall feedstock used in the subsequent Oxo-process may remain unbranched. Typically, and preferably from the standpoint of cleaning performance and biodegradability, the present process provides alpha-olefins with: an average number of branches (longest chain basis) in the 0.4-2.5 range; of the branched material, there are essentially no branches on carbons 1, 2 or on the terminal (omega) carbon of the longest chain of the branched material.
Following the formation and purification of the branched-chain alpha-olefin, the feedstock is subjected to an Oxo carbonylation process. In this Oxo-step, a catalyst (e.g., conventional cobalt carbonyl; see Kirk Othmer, below) which does not move the double bond from its initial position is used. This avoids the formation of vinylidene intermediates (which ultimately yield less favorable surfactants) and allows the carbonylation to proceed at the #1 and #2 carbon atoms.
All percentages, ratios and proportions herein are by weight, unless otherwise specified. All documents cited herein are, in relevant part, incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTIONAs can be seen from the foregoing, the present invention thus encompasses, in a process for preparing surfactant precursor hydrophobes from hydrocarbon feedstocks by the conversion of a coal or other hydrocarbon source to a mixture of carbon monoxide and hydrogen and the subsequent conversion of the carbon monoxide and hydrogen into a mixture of linear and branched hydrocarbons, the improvement which comprises abstracting from said mixture of linear and branched hydrocarbons the sub-set of branched hydrocarbons of the general formula: ##STR1## wherein x is at least about 2, y is greater than or equal to 0 and wherein the sum of x+y is at least about 7.
The invention also encompasses, in a process for preparing surfactant precursor hydrophobes from coal or other hydrocarbon feedstocks by the conversion of such feedstocks to a mixture of carbon monoxide and hydrogen and the subsequent conversion of the carbon monoxide and hydrogen into a mixture of linear and branched hydrocarbons, the improvement which comprises abstracting from said mixture of linear and branched hydrocarbons the sub-set of branched hydrocarbons of the general formula: ##STR2## wherein p is at least about 2, q is 1 to 12, r is greater than or equal to 0 and the sum of p, q and r is at least about 6.
The invention also encompasses, in a process for preparing surfactant precursor hydrophobes from coal or other hydrocarbon feedstocks by the conversion of such feedstocks to a mixture of carbon monoxide and hydrogen and the subsequent conversion of the carbon monoxide and hydrogen into a mixture of linear and branched hydrocarbons, the improvement which comprises abstracting from said mixture of linear and branched hydrocarbons the set of branched hydrocarbons comprising a mixture of:
(a) the sub-set of mono-methyl branched compounds of the formula: ##STR3##
(b) the sub-set of di-methyl branched compounds of the formula: ##STR4##
The foregoing branched hydrophobes can then be converted into the corresponding branched-chain detersive surfactants, in the manner disclosed hereinafter.
ProcessSynthesis gas (carbon monoxide/hydrogen) can be produced from coal or other hydrocarbon feedstocks such as natural gas and used to build-up various saturated and unsaturated linear, branched and cyclic hydrocarbons using conventional Fischer-Tropsch (F-T) chemistry. Such processes can be used to make a range of hydrocarbons to meet the gasoline, diesel and jet fuel needs. Two points with regard to the present invention are: first, recognition that branching occurs in F-T chemistry through free radical, not carbonium ion chemistry. This leads to isolated methyl branches with no gem-dimethyl, little ethyl and low levels of vicinal-dimethyl branches. Low pressure/low temp (i.e. wax producing) F-T chemistry builds up methylenes mostly in a linear fashion with typically about 1 methyl branch per 50 carbons. At higher pressures and/or higher temperatures (such as used for gasoline production) 1 methyl branch per 8 carbon atoms can be achieved. The rearrangement to form the methyl branch, which occurs adjacent to catalyst, can be thought of a hydrogen atom shift from the beta methylene to the alpha methylene converting it to the methyl branch. Catalyst (Fe, Co, Ru, etc.) moves from alpha to beta and with insertion of additional methylene(s) between catalyst and the methine group (former beta), isolation of the methyl branch is complete. The second key point is that alpha olefins can be a major product of F-T chemistry.
The present invention makes use of such observations to provide an overall method for preparing mid- or near-mid chain branched alpha-olefins which can be converted to the corresponding detersive surfactants, either directly or through the formation of intermediate compounds (e.g., branched-chain alcohols) which are subsequently converted into surfactants. Importantly, the surfactants thus made contain little or no contaminants such as the geminal or vicinal branches or multiple chain branches (i.e., more than about 3 branches). On a weight basis, such contaminants can detract from overall detergency performance and/or biodegradability of the final surfactant products herein.
The overall process herein is as follows:
The Fischer-Tropsch process is described in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Volume 12, pp. 157-164 (), Jacqueline I. Kroschwitz, Executive Editor, Wiley-Interscience, N.Y. The Oxo process to make alcohols is described in detail in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Volume 1, pp. 903-8 ().
1) Synthesis gas, a mixture of carbon monoxide/hydrogen is typically generated from coal or natural gas, however petroleum or other hydrocarbon sources could in principle be utilized. Air or oxygen is used to partially burn gas, petroleum, etc., to a mixture of carbon monoxide and hydrogen. Similarly, coal or coke can undergo the coke-water-gas reaction to form carbon monoxide and H2. The water gas shift reaction can be used to change the carbon monoxide/hydrogen ratio as required. Various standard cleanup steps are included to remove carbon dioxide, hydrogen sulfide, ammonia etc.
Gas+air or O2 &#;CO/H2 mixture
C+H2 O&#;CO+H2 coke-water-gas reaction
CO+H2 O&#;H2 +CO2 (water gas shift)
2) Fischer-Tropsch (F-T) chemistry is used to convert synthesis gas into a mostly hydrocarbon mixture. Conditions can be set to produce a mostly linear olefin mixture with a limited number of methyl branches as well as some cyclic hydrocarbons. Small amounts of other classes of compounds such as alcohols are also formed. Their levels can be somewhat controlled by F-T conditions; in any event they can be removed.
CO/H2 &#;Syn Fuel Mixture+Branched Alpha-Olefins
3) Distillation and other standard techniques are used to isolate the desired MW hydrocarbon fraction containing alpha-olefins. Molecular sieving can be used to separate most of the linear alpha-olefins and cyclics from the desired, limited methyl-branched, linear alpha-olefins. Standard methods utilizing zeolites can accomplish the former. Processing with zeolite sieves can be arranged to remove iso and anteiso (omega-1) and (omega-2) methyl alpha olefins, if so desired. Aliphatic hydrocarbons containing 2 geminal Me groups or highly branched aliphatic hydrocarbons (including cyclics) can be separated from aliphatic hydrocarbons containing Me groups on different C atoms and less branched aliphatic hydrocarbons by selective adsorption of the latter on a molecular sieve (pore diam. 4.4-5.0 A°) and/or from pyrolyzed poly(vinylidene chloride) (Saran) to yield gasoline with improved octane numbers; see Neth Appl. Oct. 25, , Chem. Abstracts 76:.
Syn Fuel Mixture&#;Branched alpha-Olefins
4) Oxo chemistry (CO/H2) is used to convert the branched alpha-olefin to the corresponding branched primary alcohol. Any Oxo catalyst which leads directly to alcohols or indirectly through an additional step of hydrogenation of intermediate aldehyde can be used. 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 using cobalt-carbon monoxide-organophosphine catalysts in the one step process. Conventional cobalt Oxo catalysts such as cobalt-carbon monoxide used in the two step high pressure process do not isomerize the C&#;C double bond. The fact these can give approximately equal carbonylation on 1- and 2-carbon positions of the alpha olefin is entirely acceptable. In other words the product mixture would be RCH2 CH2 CH2 OH+RCH(CH3)CH2 OH where R is linear fatty chain with limited methyl branching at the mid- or near-mid chain region.
Branched Alpha-olefins&#;Branched Primary Alcohols
5) In one aspect of the last step, any standard sulfation technique may be used to convert the above branched alcohol to a branched alcohol sulfate. Examples are sulfur trioxide in a falling film reactor or sulfur trioxide or chlorosulfonic acid in a batch reactor. In any case the acid mixture is promptly neutralized with caustic soda, or the like.
Branched Primary Alcohol&#;Branched Alkyl Sulfate
Other fatty alcohol-derived surfactants can also be made, e.g., alkyl ethoxyl sulfates (AES), alkyl polyglucosides (APG), etc. Note that surfactants other than alcohol sulfates or AES may be made by oxidizing said alcohol or its aldehyde intermediate into a carboxylate (i.e., a branched-chain soap). This soap can be an excellent surfactant and/or detergent builder in and of itself. This carboxylate can also be used as a feedstock and converted to branched acyl-aurates, -isethionates, -sarcosinates, -N-methylglucamides or other similar acyl-derived surfactants, using art-disclosed techniques.
INDUSTRIAL APPLICABILITYBranched-chain surfactants of the type resulting from the present process can be used in all manner of cleaning compositions. Such compositions include, but are not limited to: granular, bar-form and liquid laundry detergents; liquid hand dishwashing compositions; liquid, gel and bar-form personal cleansing products; shampoos; dentifrices; hard surface cleaners, and the like. Such compositions can contain a variety of conventional detersive ingredients. The following listing of such ingredients is for the convenience of the formulator, and not by way of imitation of the types of ingredients which can be used with the branched-chain surfactants herein.
The branched-chain surfactants herein can be used in combination with detergency builders. Such builders include, for example, 1-10 micrometer zeolite A, polycarboxylate builders such as citrate, layered silicate builders such as "SKS-6" (Hoechst) and phosphate materials, especially sodium tripolyphosphate ("STPP"). Most laundry detergents typically comprise at least about 1% builder, more typically from about 5% to about 80% builder or mixtures of builders.
Enzymes, such as proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof, can be employed in detergent compositions containing the branched-chain surfactants. Typical detergent compositions comprise from about 0.001% to about 5% of commercial enzymes.
Detergent compositions can also contain polymeric soil release agents (SRA's). Such materials include, for example, anionic, cationic and non-charged monomer units, especially polyester materials. Preferred materials of this type include oligomeric terephthalate esters, sulfonated substantially linear ester oligomers comprising a backbone of terephthaloyl and oxyalkyleneoxy repeat units and phthalolyl-derived sulfonated terminal moieties. A variety of SRA's are described, for example, in U.S. Pat. Nos. 4,968,451; 4,711,730; 4,721,580; 4,702,857; 4,877,896; 5,415,807; and in other literature references. Such soil release materials typically comprise from about 0.01% to about 10% of finished detergent compositions.
Detergent compositions may also optionally contain bleaching compositions comprising a bleaching agent and one or more bleach activators. If present, bleaching agents such as percarbonate or perborate (especially perborate monohydrate "PB1") typically are used at levels from about 1% to about 30% of finished detergent compositions. Bleach activators such as nonanoyloxy-benzene sulfonate ("NOBS") and tetraacetyl ethylenediamine ("TAED"), and mixtures thereof, can be used to enhance the bleaching activity of materials such as perborate and percarbonate. If present, the amount of bleach activator will typically be from about 0.1% to about 60% of a bleaching composition comprising a bleaching agent-plus-bleach activator. Other bleaching agents such as the so-called "photoactivated" bleaches (see U.S. Pat. No. 4,033,718) can also be used. Sulfonated zinc phthalocyanine is an especially preferred photoactivated bleaching agent.
Detergent compositions can also contain clay soil removal/antiredeposition agents such as ethoxylated tetraethylene pentamine; see U.S. Pat. No. 4,597,898. Such materials typically comprise from about 0.01% to about 10% of fully-formulated laundry detergents.
Detergent compositions can also contain from about 0.1% to about 7% of polymeric dispersing agents, which are especially useful in the presence of zeolite and/or layered silicate builders. Such materials are known in the art (see U.S. Pat. No. 3,308,067). Such materials include acrylate/malic-based copolymers, such as described in EP 193,360, as well as polyethylene glycol ("PEG").
Detergent compositions herein can also include various brighteners, dye transfer inhibiting agents (especially polymers of N-vinylpyrrolidone and N-vinylimidazole), suds suppressors (especially silicones), chelating agents such as nitrilotriacetate, ethylenediamine disuccinate, and the like. Such materials will typically comprise from about 0.5% to about 10%, by weight, of fully-formulated cleaning compositions.
Moreover, it is to be understood that the branched-chain surfactants prepared in the manner of the present invention may be used singly in cleaning compositions or in combination with other detersive surfactants. Typically, fully-formulated cleaning compositions will contain a mixture of surfactant types in order to obtain broad-scale cleaning performance over a variety of soils and stains and under a variety of usage conditions. One advantage of the branched-chain surfactants herein is their ability to be readily formulated in combination with other known surfactant types. Nonlimiting examples of additional surfactants which may be used herein typically at levels from about 1% to about 55%, by weight, include the unsaturated sulfates such as oleyl sulfate, the C10 -C18 alkyl alkoxy sulfates ("AEX S"; especially EO 1-7 ethoxy sulfates), C10 -C18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C10-18 glycerol ethers, the C10 -C18 alkyl polyglycosides and their corresponding sulfated polyglycosides, and C12 -C18 alpha-sulfonated fatty acid esters. Nonionic surfactants such as the ethoxylated C10 -C18 alcohols and alkyl phenols, (e.g., C10 -C18 EO (1-10) can also be used. If desired, other conventional surfactants such as the C12 -C18 betaines and sulfobetaines ("sultaines"), C10 -C18 amine oxides, and the like, can also be included in the overall compositions. The C10 -C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12 -C18 N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10 -C18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12 -C18 glucamides can be used for low sudsing. C10 -C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10 -C16 soaps may be used. C10 -C14 alkyl benzene sulfonates (LAS), which are often used in laundry detergent compositions, can also be used with the branched surfactants herein.
The following Examples illustrate the use of branched-chain surfactants prepared according to the present invention in various cleaning compositions, but is not intended to be limiting thereof.
EXAMPLE IGranular laundry detergents are prepared as follows.
______________________________________
A B C
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Blown Powder
Zeolite A 30.0 22.0 6.0
Sodium sulfate 19.0 5.0 7.0
Polyacrylate
LAS 13.0 11.0 21.0
Branched AS* 9.0 8.0 8.0
Silicate, Na -- 1.0 5.0
Soap -- -- 2.0
Carbonate, Na 8.0 16.0 20.0
Spray On
C.sub.14-15 EO7 1.0 1.0 1.0
Dry additives
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.1 0.1 0.1
Cellulase 0.1 0.1 0.1
NOBS -- 6.1 4.5
PB1 1.0 5.0 6.0
Sodium sulfate -- 6.0 --
Moisture & Miscellaneous
Balance
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*C.sub.12C.sub.14 methyl branched alkyl sulfate, prepared as disclosed
above.
A bleach-containing nonaqueous liquid laundry detergent is prepared as follows.
EXAMPLE II
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Wt.
Component % Range (% wt.)
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Liquid Phase
Branched AS* 25.3 18-35
C.sub.12-14, EO5 alcohol ethoxylate 13.6 10-20
Hexylene glycol 27.3 20-30
Perfume 0.4 0-1.0
Solids
Protease enzyme 0.4 0-1.0
Na.sub.3 Citrate, anhydrous 4.3 3-6
Sodium perborate (PB-1) 3.4 2-7
Sodium nonanoyloxybenzene sulfonate (NOBS) 8.0 2-12
Sodium carbonate 13.9 5-20
Diethyl triamine pentaacetic acid (DTPA) 0.9 0-1.5
Brightener 0.4 0-0.6
Suds Suppressor 0.1 0-0.3
Minors Balance
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*C.sub.12C.sub.16 methyl branched alkyl sulfate, Na salt, prepared as
disclosed above.
A hand dishwashing liquid is as follows.
EXAMPLE III
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______________________________________ Ingredient % (wt.) Range (% wt.) ______________________________________ Branched AS* 13.0 5-15 Ammonium C.sub.12-13 alkyl ethoxy sulfate 15.0 10-35 Coconut amine oxide 2.6 2-5 Betaine**/Tetronic 704 ® 0.87-0.10 0-2 (mix) Alcohol Ethoxylate C.sub.8 E.sub.11 5.0 2-10 Ammonium xylene sulfonate 4.0 1-6 Ethanol 4.0 0-7 Ammonium citrate 0.06 0-1.0 Magnesium chloride 3.3 0-4.0 Calcium chloride 2.5 0-4.0 Ammonium sulfate 0.08 0-4.0 Hydrogen peroxide 200 ppm 0-300 ppm Perfume 0.18 0-0.5 Maxatase ® protease 0.50 0-1.0 Water and minors Balance ______________________________________ *C.sub.12 C.sub.14 methyl branched alkyl sulfate, triethanolammonium salt prepared as disclosed above. **Cocoalkyl betaine.