Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
  • C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups

Definitions

• This invention relates to arylalkylsulfonic acids and new and improved processes for the preparation of arylalkylsulfonic acids derived from aromatic or substituted aromatic molecules and alpha olefin sulfonic acid (“AOS acid”; generally a mixture of alkenesulfonic acid and sultones, produced from the sulfonation of alpha olefins). More particularly, the invention relates to the use of a superacid catalyst (or an effective alkylation promoter) to effectuate the conversion of AOS acid and aromatic reactants to arylalkylsulfonic acid under substantially anhydrous conditions.
• AOS acid alpha olefin sulfonic acid
• the processes of the invention generally do not require an AOS acid conversion step (i.e., conversion whereby water is added and removed, along with heating, to and from the crude AOS acid to convert sultones to alkene sulfonic acid) prior to alkylation, nor is there a requirement of digesting the AOS prior use in the alkylation process. Further, the invention allows for achievement of higher selectivity (i.e., monoalkylation versus undesirable polyalkylation and/or AOS acid dimerization/oligomerization) via use of excess aromatic reactants, while at the same time achieving excellent reaction rates.
• AOS acid conversion step i.e., conversion whereby water is added and removed, along with heating, to and from the crude AOS acid to convert sultones to alkene sulfonic acid
• the invention allows for achievement of higher selectivity (i.e., monoalkylation versus undesirable polyalkylation and/or AOS acid dimerization/oligomerization) via use of excess aromatic reactants, while at the
• Alkylbenzene sulfonic acids and the corresponding sulfonates have found wide spread use as surfactants in a variety of detergent, emulsion and industrial applications. These materials typically comprise a substituted aromatic ring, with an alkyl group at one position on the ring and a sulfonic acid moiety attached to another position on the ring; polyalkylates may also be present.
• alkylbenzene sulfonates based on branched alkyl groups.
• Linear alkylbenzenes starting materials which are based on the reaction of linear olefins (see, e.g., U.S. Pat. No. 3,585,253; to Huang, Jun. 15, 1971) or linear chloroparaffins (see, e.g., U.S. Pat. No. 3,355,508; to Moulden, Nov. 28, 1967) with benzene in the presence of a Lewis Acid catalyst are also well known in the surfactant art. These materials possess excellent detergency properties and are rapidly biodegradable. More recently, HF (or the Detal process variation) has become the alkylation catalyst of choice for the preparation of alkylated benzenes and other alkylated aromatic compounds, based upon environmental objections to the use of AlCl 3 .
• alkylbenzene sulfonates are also employed in considerable quantities as additives in lubricants, coolants, industrial surfactant formulations, dispersants, emulsifiers, corrosion inhibitors and demulsifiers.
• Alkylbenzene sulfonates find widespread use in many industries among which are the petroleum recovery, refining, emulsion polymerization, textile dyeing, agriculture, institutional cleaning, drilling fluids, paper processing, coatings, and adhesives industries.
• alkyl xylene sulfonates see, e.g., EP121964
• dialkyl phenol polyethoxy alkyl sulfonates see, e.g., U.S. Pat. No. 4,220,204; to Hughes, et. al., Sep. 2, 1980
• U.S. Pat. No. 6,043,391; to Berger, et. al., Mar. 28, 2000 disclosed new sulfonic acid materials and processes for producing di- and tri-alkylbenzenes where both linear and branched alkyl groups are present on the same benzene ring.
• Alkoxylated alkyl substituted phenol sulfonates have been produced and found to be useful as surfactants in numerous applications (see, e.g., U.S. Pat. No. 5,049,311; to Rasheed, et. al., Sep. 17, 1991, listing many uses for these compounds including use in enhanced oil recovery processes, as corrosion inhibitors, hydrotropes, foaming agents in concrete formation, surfactants for dye carriers, surfactants for fiber lubricants, surfactants for emulsion polymerization, as textile detergents, as foaming agents for drilling fluids, and as agricultural emulsifiers).
• Alpha-olefin sulfonates are widely used as surfactants in personal care, emulsion polymerization and fire-fighting foam applications, as well as a wide variety of other uses. These materials are typically produced on a commercial scale by sulfonating an alpha-olefin with SO 3 , in a falling film sulfonator (see, e.g., Weil, Stirton and Smith; JOACS Vol 42, October 1965, pp 873-875, describing the reaction of hexadecene-1 and octadecene-1 with SO 3 followed by neutralization with NaOH to form the corresponding hexadecene sulfonates).
• the AOS precursor alpha-olefin sulfonic acid typically comprises alkene sulfonic acid and various sultones.
• AOS correspondingly does not comprise a single component, but predominantly a mixture of two materials: an alkene sulfonate and a hydroxyalkane sulfonate.
• the hydroxyalkane sulfonate is present due to the formation of intermediate sultones when SO 3 reacts with the alpha olefin.
• Neutralization with NaOH for example, not only neutralizes the alkene sulfonic acid formed during the sulfonation reaction, but also opens the sultone ring forming additional alkene sulfonate and hydroxyalkane sulfonate. This results in a final product comprising approximately 60-70% alkene sulfonate, approximately 30% 3-, and 4-hydroxy sulfonate and approximately 0-10% disulfonate material; these percentages can vary greatly depending on the sulfonation and neutralization conditions which are utilized.
• crude alkene sulfonic acid (containing significant amounts of sultone) produced from the reaction of an alpha-olefin and SO 3 , is subjected to the aforementioned water addition and removal process for conversion of sultone to alkene sulfonic acid, which is then used to alkylate a variety of aryl compounds such as benzene, naphthalene, or substituted benzene and naphthalenes.
• sulfonate functional group i.e., —SO 3 —
• suitable starting materials must contain at least about 5 nonaromatic carbon atoms per molecule, a sulfonate functional group, i.e., —SO 3 —, and one of the following: (1) a carbon-carbon double bond, i.e., —CH ⁇ CH—; (2) an alkanol hydroxy group, or a sulfonate ester group of which the above sulfonate group is a component, i.e., a sultone, and the functional groups must be substituents attached to non-aromatic carbon atoms with the balance being carbon and/or hydrogen.
• This invention relates to arylalkylsulfonic acids and new and improved processes for the preparation of arylalkylsulfonic acids derived from aromatic (or substituted aromatic) molecules and AOS acid. It has been surprisingly discovered that crude AOS acid, which contains an appreciable amount of sultone material, can be directly converted to arylalkylsulfonic acids, without the use of water addition/removal conversion cycles.
• the invention relates to the use of a superacid catalyst (or an alkylation promoter) to effectuate the conversion of AOS acid and aromatic reactants to arylalkylsulfonic acid under substantially anhydrous conditions, whereby a substantial improvement in the rate (and monoalkylation selectivity) of conversion of the reactants to arylalkylsulfonic acid is realized, as compared to methods of preparation previously known.
• the processes of the invention generally do not require an AOS acid conversion step (i.e., conversion, whereby water is added and removed in a repeated cyclic fashion, along with heating, to and from the crude AOS acid to convert the sultone to alkene sulfonic acid) prior to alkylation. Additionally, the processes of the invention do not require that the AOS acid be digested (defined hereinafter) prior to use in the alkylation reaction.
• the invention encompasses a method for preparing an arylalkylsulfonic acid comprising alkylating an aromatic compound with an AOS acid in the presence of a superacid catalyst at a temperature sufficient to produce an arylalkylsulfonic acid, wherein the alkylation is conducted under substantially anhydrous conditions.
• the aromatic compound is selected from the group consisting of benzene, a mono-substituted aromatic compound, a poly-substituted aromatic compound, alkylbenzene, alkoxylated benzene, a polycyclic aromatic compound, a mono-substituted polycyclic aromatic compound, a poly-substituted polycyclic aromatic compound, naphthalene and alkylnaphthalene, or a mixture thereof.
• the AOS acid typically comprises an alkene sulfonic acid, a sultone or a mixture thereof.
• the AOS acid may also be predominantly sultone material.
• the superacid catalyst is generally selected from the group consisting of a solid super-acid, a perfluorosulfonic acid resin (e.g., Nafion® NR50, a registered trademark of E. I. duPont de Nemours Co.), a supported perfluorosulfonic acid resin, a metal sulfate, zirconium sulfate, zirconium tungstate, a superacid zeolite, a sulfated metal oxyhydroxyide, a sulfated metal oxysilicate, a superacid metal oxide, CF 3 SO 3 H or a mixture thereof.
• a perfluorosulfonic acid resin e.g., Nafion® NR50, a registered trademark of E. I. duPont de Nemours Co.
• a supported perfluorosulfonic acid resin e.g., a metal sulfate, zirconium sulfate, zircon
• the processes of the invention generally do not require an AOS acid conversion step.
• the method can optionally further comprise digesting (distinct from conversion and defined hereinafter) the AOS acid, optionally in the presence of water, and optionally in the presence of the aromatic compound, and if present, removing said water prior to alkylation, such that the alkylation is conducted under substantially anhydrous conditions.
• the processes of the invention may also comprise alkylating the aromatic compound with an AOS 0.15 acid in the presence of an alkylation promoter comprising the arylalkylsulfonic acid itself, i.e., a reaction heel, either from a previous preparation or prepared concurrently in the process being practiced.
• an alkylation promoter comprising the arylalkylsulfonic acid itself, i.e., a reaction heel, either from a previous preparation or prepared concurrently in the process being practiced.
• These embodiments may also include the use of a superacid catalyst in combination with the alkylation promoter.
• reaction of AOS acid with an aromatic compound in the presence of the superacid catalyst (or arylalkylsulfonic acid alkylation promoter heel), may be carried out in batch mode, semi-continuous or in a continuous flow process such as provided by, for example, a continuous stirred tank reactor.
• the new processes generally afford arylalkylsulfonic acids with substantially higher conversion yields, highly desirable lighter color and reduced odor, as compared to previously known methods for preparing such acids.
• the invention allows for achievement of higher selectivity (i.e., monoalkylation) via use of excess aromatic, while at the same time achieving excellent reaction rates.
• This discovery is especially surprising, as in previously known methods, the use of excess aromatic dramatically slows reaction rates such that the reaction is not commercially practical or such that very high reaction temperatures are needed, resulting in very poor product color and odor.
• the invention provides a method for preparing an arylalkylsulfonic acid comprising alkyating an aromatic compound with an AOS acid in the presence of a superacid catalyst and at a temperature sufficient to produce an arylalkylsulfonic acid, wherein the alkylation is conducted under substantially anhydrous conditions.
• the molar ratio of aromatic compound to AOS acid is from about 1:1 to about 30:1.
• the molar ratio of aromatic compound to AOS acid is from about 2:1 to about 10:1.
• the aromatic compound is generally selected from the group consisting of benzene, a mono-substituted aromatic compound, a poly-substituted aromatic compound, alkylbenzene, alkoxylated benzene, a polycyclic aromatic compound, a mono-substituted polycyclic aromatic compound, a poly-substituted polycyclic aromatic compound, naphthalene and alkylnaphthalene, or a mixture thereof. More specifically, the aromatic compound is selected form the group consisting of benzene, toluene, xylene, cumene, ethyl benzene, propylbenzene and naphthalene, or a mixture thereof.
• the aromatic compound is benzene or toluene.
• the aromatic compound may also be selected from the group consisting of phenol, alkylphenol, alkoxylated phenol, and alkoxylated alkylphenol, or a mixture thereof.
• the AOS acid generally comprises an alkene sulfonic acid, a sultone or a mixture thereof.
• the sultone is generally of the formula:
• alkene sulfonic acid is generally of the formula:
• a is 1, 2 or 3 and b is an integer 1 to 31; wherein c and d are independently integers 0 to 33, provided that c+d 1 to 33.
• the molar ratio of alkene sulfonic acid to sultone is from about 1:1 to about 1:4.
• the superacid catalyst is selected from the group consisting of a solid superacid, a perfluorosulfonic acid (e.g., Nafion® NR50) or a resin thereof, a superacid zeolite, a supported perfluorosulfonic acid resin, a metal sulfate, zirconium sulfate, zirconium tungstate, a sulfated metal oxyhydroxyide, a sulfated metal oxysilicate, a superacid metal oxide, CF 3 SO 3 H, or a mixture thereof.
• the perfluorosulfonic acid resin is a copolymer of sulfonyl fluorovinyl ether and a fluorocarbon.
• the arylalkylsulfonic acid comprises a compound of the formula:
• m and n are independently integers 0 to 34, provided that m+n is at least 2 and wherein m+n is equal to or less than 34; wherein R and R′ are independently branched or straight chain C 1-36 alkyl or substituted alkyl.
• processes of the invention provide this material as the primary component in excess of 30% by weight, and ideally in excess of 50% by weight, based on the total weight of the arylalkylsulfonic acid.
• the arylalkylsulfonic acid may further comprise a compound of the formula:
• m and n are independently 0-34, provided that m+n is at least 2 and wherein m+n is equal to or less than 34; wherein o and p are independently 0-34, provided that o+p is at least 2 and wherein o+p is equal to or less than 34; wherein R and R′ are independently branched or straight chain C 1-36 alkyl or substituted alkyl.
• processes of the invention provide this material as aminor component relative to the monoalkalkylate material.
• the arylalkylsulfonic acid may further comprise an AOS acid dimer compound of the formula:
• a and b are independently 0-34, provided that a+b is at least 2 and wherein a+b is equal to or less than 34; wherein c and d are independently 0-34, provided that c+d is at least 2 and wherein c+d is equal to or less than 34.
• the alkylation processes detailed herein are conducted at a temperature from about 80° C. to about 200° C.; the alkylation is always conducted at a temperature below the decomposition temperature of the reactants or products. Ideally, the alkylation is conducted at a temperature from about 100° C. to about 150° C.
• the invention further provides a method for preparing an arylalkylsulfonic acid, comprising:
• the aromatic compound is selected from the group of materials previously defined above, with the AOS to aromatic ratio as previously defined.
• the AOS acid comprises an alkene sulfonic acid, a sultone or a mixture thereof, as previously discussed; the sultones and alkene sulfonic acids are of the formulas and present in the ratios as detailed above.
• the superacid catalysts useful in accordance with this embodiment are the same as those previously described; the temperature at which the alkylation is conducted is as previously detailed. Additionally, the arylalkylsulfonic acid comprises compounds similar to those described above.
• the alpha olefins useful in this embodiment are of the formula
• n 1-33.
• branched olefins may be used, as well as internal olefins which are either linear or branched; vinylidines may also be used.
• the invention provides a method for preparing an arylalkylsulfonic acid comprising alkylating an aromatic compound with an AOS acid in the presence of an alkylation promoter comprising a compound of the formula:
• m and n are independently integers 0 to 34, provided that m+n is at least 2 and wherein m+n is equal to or less than 34; wherein R and R′ are independently branched or straight chain C 1-36 alkyl or substituted alkyl, wherein the alkylation is conducted at a temperature sufficient to produce an arylalkylsulfonic acid; and wherein the alkylation is conducted under substantially anhydrous conditions; and wherein the alkylation promoter is present in at least about 25% by weight, based on the weight of the AOS acid. Ideally, the alkylation promoter is present in at least a 1:1 ratio with the AOS acid.
• the alkylation promoter is present in at least a 2:1 ratio with the AOS acid.
• the alkylation promoter may be prepared in situ during an alkylation reaction or may originate from a previous arylalkylsulfonic acid formation reaction.
• the term “alkylation promoter” as used herein means the materials described above and below, wherein such materials are very strong anhydrous acid materials which are capable of effectuating the alkylation reaction to produce an arylalkylsulfonic acid with the requisite properties, i.e., selectivity, yield, color, etc.
• the alkylation promoter may further comprise a compound of the formula:
• m and n are independently 0-34, provided that m+n is at least 2 and wherein m+n is equal to or less than 34; wherein o and p are independently 0-34, provided that o+p is at least 2 and wherein o+p is equal to or less than 34; wherein R and R′ are independently branched or straight chain C 1-36 alkyl or substituted alkyl.
• the alkylation promoter may comprise a compound of the formula:
• this dimer acid material may contain a cyclic type structure as previously discussed above, and/or may be oligomeric in nature.
• the AOS acid comprises an alkene sulfonic acid, a sultone, with the structures/formulas for such materials being as previously defined, or a mixture thereof.
• the alkylation promotion agent may further comprise a superacid catalyst, such as those previously described.
• the invention provides a method for preparing an arylalkylsulfonic acid comprising
• alkylating an aromatic compound with the AOS acid in the presence of an alkylation promoter wherein the alkylation is conducted at a temperature sufficient to produce an arylalkylsulfonic acid, and wherein the alkylation is conducted under substantially anhydrous conditions.
• the alpha olefin, alkene sulfonic acid, sultone, the alkylation promoter and arylalkylsulfonic acid are as previously defined.
• This embodiment may further comprise the use of a previously identified superacid catalyst in combination with the alkylation promoter.
• the invention provides arylalkylsulfonic acids produced by the processes identified herein.
• the aromatic compound may generally be any compound which is capable of being alkylated with an alkene sulfonic acid (which comprises alkene sulfonic acid molecules and sultones, or alternatively a material which predominently comprises sultones).
• an alkene sulfonic acid which comprises alkene sulfonic acid molecules and sultones, or alternatively a material which predominently comprises sultones.
• the aromatic compound can be any one of those identified and produced in U.S. Pat. Nos. 5,146,026; Berna Tejero, et. al., Sep. 8, 1992; 6,129,219; Kojima, et. al., Jan. 2, 2001; 5,157,158; Berna Tejero, et. al., Oct. 20, 1992; Waller, F.
• naphthalene and any other polycyclic aromatics may be substituted for benzene, and where none is defined as no substitution in the structure and where R 1 , R 2 and R3 are independently none, alkyl (branched or linear C 1-36 ), or alkyloxy (derived from ethylene-, propylene- or butylene-oxide, or a mixture thereof), provided that any alkoxy group is stable to the highly acidic processing conditions. Branching of the alkyl group(s) may be in present in a variety of positions and as generally described in WO 00/43478; Scheibel, et. al.; pub. Jul. 27, 2000, incorporated herein by reference.
• AOS acid (or alpha olefin sulfonic acid) means an acid material which is the reaction product of sulfonating an olefin, typically an alpha olefin, and generally comprises an alkene sulfonic acid, a sultone or a mixture thereof (the formulas for such materials are as previously described).
• Alkene sulfonic acid (or AOS acid which contains an appreciable amount of alkene sulfonic acid) is the precursor to alpha-olefin sulfonate or AOS which is a widely used surfactant with many applications for foaming, cleaning, emulsifying, and wetting.
• AOS acid is typically produced through the reaction of SO 3 with mono-olefinic hydrocarbon, as shown for example, in U.S. Pat. Nos. 2,061,617; 2,572,605; and 3,444,191, all incorporated in the entirety herein.
• a process for producing high yields of alkene sulfonic acids is found in Weil, et. al., JAOCS, Vol. 41, October 1965, pp 873-875.
• the ratio of alkene sulfonic acid to sultone is from 1:1 to about 1:4 depending on manufacturing temperature, pressure, flow rates and other parameters known to those skilled in the art.
• the position of the double bond of the alkene sulfonic acid and the number of carbons in the sultone ring can also vary depending on these same parameters.
• sultone based AOS acid i.e., sultone which contains no alkene sulfonic acid or only trace amounts (less than 2 weight percent) of alkene sulfonic acid can be utilized in the alkylation methods described herein.
• the processes of the invention generally do not require an AOS acid conversion step.
• conversion is defined as the addition and removal of water in a cyclic fashion, with the application of heat (i.e. the crude acid is heated to just below its decomposition temperature), to and from the crude AOS acid to convert the sultone present in the crude acid mixture to alkene sulfonic acid prior to alkylation.
• the methods described can optionally further comprise digesting the AOS acid, optionally in the presence of water, and optionally in the presence of the aromatic compound, and removing said water prior to alkylation, such that the alkylation is conducted under substantially anhydrous conditions.
• digestion is defined a thermal heating of alkene sulfonic acid (or sultone relative to the alkene sulfonic acid), for a limited period of time (i.e., about 1-120 minutes) at a temperature less than the decomposition temperature of the acid (i.e. 40-200° C.).
• a limited period of time i.e., about 1-120 minutes
• water is not added and removed in a cyclic manner, as is the case with conversion.
• digestion does not necessarily convert sultones to alkenes as is achieved with conversion; generally in the absence of water, thermal digestion actually may convert alkene sulfonic acids to sultones, an opposite effect of conversion.
• olefin starting materials, superacid catalysts and crude alkene sulfonic acids may be somewhat hygroscopic and inherently contain trace amounts of water. Accordingly, the term “substantially anhydrous” as used herein for describing alkylation conditions denotes reaction mixtures which are basically free of added water, excepting trace amounts which are typically associated with the process reactants. Quantitatively, the term “substantially anhydrous” generally denotes a material which contains less than about 1% by weight of water, based on the weight of the crude AOS acid utilized.
• the superacid catalysts useful herein are generally any superacid catalyst which is capable of catalyzing alkylation an aromatic compound with an AOS acid at a temperature sufficient to produce an arylalkylsulfonic acid, wherein the alkylation is conducted under substantially anhydrous conditions.
• the superacid catalyst can be any one of those identified in U.S. Pat. Nos. 5,146,026; Berna Tejero, et. al., Sep. 8, 1992; 6,129,219; Kojima, et. al., Jan. 2, 2001; 5,157,158; Berna Tejero, et. al., Oct. 20, 1992; Waller, F.
• the amount of super acid cataylyst used is at least about 25% by weight, based on the amount of AOS acid.
• the superacid catalyst is present in an amount of at least 100% by weight, based on the amount of AOS acid.
• the catalyst(s) used herein may be homogeneous or heterogeneous, with the later being particularly preferred, based upon ease of separation from the product and recycleability.
• Mixtures of superacids and an alkylation promoter may be utilized.
• known very strong anhydrous acids may be utilized alone or in combination with the superacids and/or alkylation promoter previously identified, provided that such use or combination is capable of catalyzing the alkylation of an aromatic compound with an AOS acid at a temperature sufficient to produce a predominantly monoalkylated arylalkylsulfonic acid, wherein the alkylation is conducted under substantially anhydrous conditions, without the need for conversion of the starting AOS acid.
• Suitable optional very strong acid catalysts include any sulfonic acid type ion-exchange catalysts and catalyst resin systems which is capable of effectuation the alkylation detailed herein, such as for example, Amberlyst-15, acidic zeolites, acidic clays or a mixture thereof.
• Other effective very strong acid catalysts include marcroreticular sulfonic acid polymers such as sulfonated poly(styrene-divinylbenezene) ion exchange resins.
• the arylalkylsulfonic acids produced in accordance with the invention may be used “as is” or neutralized with a variety of bases such as NaOH, KOH, Ca(OH) 2 , MgO 2 , Ba(OH) 2 , NH 3 , monoethanol amine (MEA), diethanol amine (DEA), triethanol amine (TEA), iso-propanol amine, and other amines, or mixtures of such bases, to form the corresponding sulfonates.
• bases such as NaOH, KOH, Ca(OH) 2 , MgO 2 , Ba(OH) 2 , NH 3 , monoethanol amine (MEA), diethanol amine (DEA), triethanol amine (TEA), iso-propanol amine, and other amines, or mixtures of such bases, to form the corresponding sulfonates.
• the arylalkysulfonates are excellent surfactants, i.e., they are effective as surface and interfacial tension reducers, wetting agents, foaming agents and grease-cutting agents.
• the sulfonates can be used in cleaning and emulsion formulations, including hard surface cleaners, shampoos, body washes, liquid and powdered laundry detergent formulations, personal care cleansing formulations, water-in-oil emulsions, oil-in-water emulsions, and the like.
• the arylalkylsulfonates can be blended with other traditional surfactants, such as nonionic, cationic, anionic, and amphoteric/zwitterionic surfactants.
• the arylalkylsulfonates or blends thereof with traditional surfactants can be formulated into a variety of end use products such as personal care compositions (shampoos, body washes, soap bars, etc.), hard surface cleaners, laundry cleaning compositions (liquids, heavy duty liquids, and powders), dish cleaning compositions (light duty liquids), oil-in-water emulsions, water-in-oil emulsions, and the like. These end use products may also contain various ingredients typically associated with them.
• Amberlyst ® 15 Strongly acidic, macroreticular, sulfonated styrene-divinylbenzene copolymer ion-exchange resin; available from and a registered trademark of Rohm and Haas Co.
• This example demonstrates the utility of Nafion®) NR50 perfluorosulfonic acid resin as a catalyst for the substantially anhydrous, high-yield preparation of C 12 benzene alkylsulfonic acid from AOS acid.
• the starting crude AOS acid was a mixture of approximately 60% sultones and 40% alkene sulfonic acids.
• the reactor was heated to 1200C with a single valve of the autoclave open to atmosphere and 40 mL of benzene and benzene/water azeotrope were distilled off from the reaction mixture.
• the reaction mixture contained 10 molar equivalents of benzene relative to AOS acid.
• the open valve was then closed and the reaction mixture was heated with stirring at 1300C (30-40 p.s.i.) for 15 hours.
• the proton spectrum contained all of the expected features for C 12 benzene alkylsulfonic acid: ⁇ 7.4-6.7, multiplet, 5.0H, aromatic protons; ⁇ 3.0-2.2, several sets of multiplets, 1.0H, R CH (phenyl)R′; ⁇ 2.8, multiplet, 2.0H, R CH 2 SO 3 H; ⁇ 2.0-0.8, overlapping multiplets and triplets, alkyl CH 2 and CH 3 .
• the recovered Nafion® NR50 catalyst was used repeatedly in more than 10 reactions under conditions identical to those described above. The catalyst was found to retain full activity without change in reaction product characteristics upon recycling.
• This example demonstrates the utility of a dispersion of Nafion® NR50 on silica (i.e., Nafion® SAC-13) as a catalyst for the high-yield preparation of C 14-16 toluene alkysulfonic acid from AOS acid.
• the flask was fitted with a short-path still and 20.5 mL (0.192 mole) of toluene and toluene/water azeotrope were distilled from the solution in order to remove trace amounts of water.
• the remaining solution consisted of a 1:5 molar ratio of AOS acid to toluene.
• 26.1 g of the solution (10.0 g of AOS acid) was transferred to a 50 mL round bottom flask, equipped with reflux condenser and N 2 inlet, that contained 10.0 of Nafion® SAC-13 catalyst.
• the catalyst had been previously dried under N 2 at 150° C. for 3 hrs.
• the reaction flask was heated to a constant ⁇ 116° C. reflux for 8 h.
• the normalized proton content of 4.1 aromatic protons and 3.0 tolyl-CH 3 protons relative to RCH 2 SO 3 H compares favorably to the theoretical value of 4.0H (aromatic) and 3.0H (tolyl-CH 3 ) for 100% toluene alkylsulfonic acid.
• RCH 2 SO 3 H groups as a reference of 1 molar unit, molar quantities were calculated, recognizing that dialkylates and AOS acid dimers each contain 2 mole equivalents of sulfonic acid. These quantities were calculated as follows:
• Mole AOS dimer acid [1.0 ⁇ Mole toluene alkylsulfonic acid ⁇ (Mole dialkylate*2)]/2
• This example demonstrates the ineffectiveness of sulfuric acid as a catalyst for the reaction of C 14-16 AOS acid with toluene.
• the reaction mixture was refluxed (111° C.) and conversion was monitored in terms of acid content by titration of aliquots with 0.1 N cyclohexylamine in methanol.
• the crude sultone was crystallized at ⁇ 30° C. from hexanes (ca. 6:1 ratio hexanes to sultone), filtered while cold, and dried to afford high purity dodecene ⁇ -sultone (dodecene-1,4-sultone) as a white, crystalline solid.
• the sultone contained less than 0.1% water, as determined by Karl Fischer titration.
• Example 7 Comparison among the entries within Example 7 and within Example 8 indicates that increasing water content decreased both conversion of AOS acid and selectivity for benzene alkylsulfonic acid.
• These data exemplify the desirability of performing the reaction between AOS acid and an aromatic compound to afford arylalkylsulfonic acids under substantially anhydrous conditions.
• comparison of data between Examples 7 and 8 reveals that, even without any stirring, the presence of heterogeneous superacid catalyst improved both AOS acid conversion and selectivity for benzene alkylsulfonic acid.
• This example demonstrates the utility of a strongly acidic ion-exchange resin as a catalyst for the high-yield preparation of C 12 toluene alkylsulfonic acid from AOS acid.
• AOS crude C 12 alkene sulfonic
• This example demonstrates the utility of linear alkylbenzenesulfonic acid as a catalyst for the reaction of AOS acid with an aromatic compound to afford a mixed sulfonic acid product.
• This example demonstrates the utility of an AOS-acid digestion step prior to reaction with toluene as a means of improving the rate of reaction for the synthesis of arylalkysulfonic acid.
• To a 100 mL round bottom flask equipped with magnetic stir bar was added 15.0 g (0.0524 moles) of dry C 14-16 AOS acid. The flask was heated under N 2 at 150° C. for 1 hour. Upon cooling, 9.67 g (0.105 moles) of toluene was added, the flask was fitted with a reflux condenser and N 2 inlet, and the mixture was heated in a 130° C. oil bath until acid content had become constant.
• reaction was monitored by cyclohexylamine titration of sulfonic acid that had been generated from the conversion of sultones in the AOS acid, taking into account the sulfonic acids already present in the reaction system from alkene sulfonic acid and the promoter acid.
• Reaction conditions and approximate sultone conversion were as follows: TABLE 8 Example: 12 13 14 15 Reaction Temp. 130 130 130 130 Mole equivalents Toluene 2 2 2 5 Mole equivalents toluene alkysulfonic acid as 0.25 1.0 2.0 2.0 reaction promoter a Reaction Time(hours): Approx. % Approx. % Approx. % Approx.
• This example demonstrates the utility of repeatedly using the products of previous syntheses of benzene alkylsulfonic acid to afford products that are substantially enriched in benzene dialkylsulfonic acids.
• To a 300 mL glass-lined autoclave was added 19.75 g (0.0795 mole) of crude C 12 AOS Acid, 74 g (0.947 mole) of benzene, and 51.89 g (0.159 mole) of C 12 benzene alkylsulfonic acid that had been previously prepared via the process described in Example 1. With a single valve of the autoclave open to atmosphere, the reactor was heated to 120° C.
• reaction mixture contained 5 molar equivalents of benzene relative to AOS acid.
• the reactor was cooled, an additional 50 mL of benzene was added, and the distillation of 50 mL of benzene and benzene/water azeotrope was repeated.
• the open valve was then closed and the reaction mixture was heated with stirring at 130° C. (30-40 p.s.i.) for 4 hours.
• the product was isolated by vacuum rotary evaporation. The process was then repeated 3 times, each time using 51 grams of the product of the previous reaction to promote the reaction of 19.75 g of C 12 AOS acid with 5 mole equivalents of benzene.
• Dialkylate Integration ArH ( ⁇ 7.08 ⁇ 6.85 ppm)/4.0
• AOS dimer [3.0 ⁇ (benzene alkylsulfonic acid*3.0) ⁇ (dialkylate*6.0)]/6.0
• This example illustrates the useful surfactant properties of the sodium salts of arylalkylsulfonic acids prepared from the superacid catalyzed reaction of AOS acid with aromatic compounds.
• This example demonstrates the useful detergent properties of the sodium salts of C 12 Benzene alkylsulfonic acids enriched in dialkylates and AOS dimer acids, as prepared by the method described in Example 16.
• Aqueous solutions of sodium salts of sulfonic acids were prepared by neutralization of the acids with sodium hydroxide in de-ionized (DI) water. These surfactants were evaluated for their ability to clean artificially soiled fabrics by washing fabric swatches in 1 liter of 0.05 wt % solutions of the surfactants in 90 ppm 3:2 Ca/Mg hard water.
• a laboratory scale washing machine (Terg-o-tometer, United States Testing Co., 1415 Park Ave., Hoboken, N.J.) was utilized with the following test conditions: duplicate swatches of soiled fabrics, as specified in the table below, all swatch types combined in a single pot for a single surfactant; 100° F.
• ⁇ E [( L w ⁇ L u ) 2 +( a w ⁇ a u ) 2 +( b w ⁇ b u ) 2 ] 1/2
• Solvent-free all-purpose cleaner formulations were prepared using the ingredients listed in the table below: TABLE 14 Comparative Ingredient Example 22
• Example 23 Example F Sodium Xylene 1.38 g 1.38 g 1.39 g Sulfonale (40% Active) Tetra-sodium 0.44 0.43 0.45 EDTA a Sodium 0.22 0.21 0.21 metasilicate ⁇ 5H 2 O C 12 Benzene 0.88 — — Alkylsulfonic acid C 12 Toluene — 0.88 — Alkylsulfonic acid Ninol ® 11-CM b — — 0.88 Sodium Hydroxide 0.11 0.13 0.11 (50% aqueous) DI Water 46.96 46.97 46.94 Appearance Clear Solution Clear Solution Clear Solution pH 10.49 11.37 11.97
• Examples 22 and 23 are comparable in composition to Comparative Example F, except that Ninol® 11-CM was replace with an equivalent amount of C 12 arylalkylsulfonic acid. In all three formulations, a clear solution was obtained, indicating good compatibility of the arylalkylsulfonic acids with the other formulating components.
• Examples 24 and 25 are comparable in composition to Comparative Example G, except that Ninol® 11-CM was replace with an equivalent amount of C 12 arylalkylsulfonic acid. In all three formulations, a clear solution was obtained, indicating good compatibility of the arylalkylsulfonic acids with the other formulating components.
• Pine oil cleaner concentrate formulations were prepared using the ingredients listed in the table below. Cleaning performance on vinyl tiles at room temperature was evaluated using ASTM D 4488-95, Annex A5, “Particulate and Oily SoilNinyl Tiles Test Method.” This test used a modified Gardner Straight Line Washability Apparatus, as described in ASTM D 4488-95, Annex A4. The formulations were evaluated at 3.9 mL of concentrate diluted to 500 mL with Dl water.
• Examples 30 and 31 are comparable in composition to Comparative Example J, except that C 11-4 linear alkylbenzenesulfonic acid was replace with a similar amount of C 12 arylalkylsulfonic acid. In all three formulations, a clear solution was obtained, indicating good compatibility of the arylalkylsulfonic acids with the other formulating components.
• Examples 32 and 33 are comparable in composition to Comparative Example K, except that C 14 linear alkylbenzenesulfonic acid was replace with similar amounts of C 1-2 arylalkylsulfonic acid.
• Powdered laundry detergent formulations were prepared in a laboratory blender using the ingredients listed in the table below. Detergent performance was evaluated using a method comparable to that described in Example 21. Test conditions were: 1.5 g of formulation in 1 L of 140-150 ppm hard water (2:1 Ca/Mg); duplicate swatches of soiled fabrics, as specified in the table below, all swatch types combined in a single pot for a single formulation; 100° F. wash water; 100 RPM agitation; 10 minute wash; hand rinse for 1 minute.
• Liquid laundry detergent formulations were prepared using the ingredients listed in the table below. Detergent performance was evaluated using a method comparable to that described in Example 21. Test conditions were: 1.85 g of formulation in 1 L of 140-150 ppm hard water (2:1 Ca/Mg); duplicate swatches of soiled fabrics, as specified in the table below, all swatch types combined in a single pot for a single formulation; 100° F. wash water; 100 RPM agitation; 10 minute wash; hand rinse at 70° C.
• Liquid laundry detergent formulations were prepared using the ingredients listed in the table below. Detergent performance was evaluated using a method comparable to that described in Example 21. Test conditions were: 1.68 g of formulation in 1 L of 140-150 ppm hard water (2:1 Ca/Mg); duplicate swatches of soiled fabrics, as specified in the table below, all swatch types combined in a single pot for a single formulation; 100° F. wash water; 100 RPM agitation; 10 minute wash; hand rinse at 70° C.

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