Alkyl ether sulfate surfactants and related manufacturing methods

Abstract

The process comprises contacting an olefin, an alcohol, and a metallosilicate catalyst to form an oligomer of alcohol ethoxylate having structure (I), wherein R1 is alkyl, R2 is alkyl, and n has a value of 1 to 3; and sulfating the oligomer of structure (I) to form an oligomer of structure (II), wherein R1 is alkyl, R2 is selected from the group consisting of alkyl groups, M is selected from the group consisting of protons, ammonium cations, metal cations, nitrogen cations, boron cations, phosphorus cations, triethylamine, triethanolamine, monoethanolamine, and combinations thereof, and n has a value of 1 to 3, wherein at least 95 mole percent of the oligomers of structure (II) have an n of 1 and no more than 5 mole percent of the oligomers of structure (II) have an n of 2 or greater.

Description

[Technical Field]

[0001] FIELD OF THE INVENTION FIELD OF THE DISCLOSURE This disclosure relates generally to surfactants, and more specifically to alkyl ether sulfate surfactants and related methods of manufacture.

[0002] (Introduction) Regulatory agencies are increasing limits on the amount of 1,4 dioxane ("dioxane") that can be present in consumer products. For example, New York State has banned all but trace amounts of dioxane in cosmetics, personal care, and cleaning products. Typically, consumer products must contain less than 10 parts per million ("ppm") of dioxane to comply with regulations. One contributor to dioxane in consumer products can be alkyl ethoxy sulfate ("AES") anionic surfactants.

[0003] Dioxane formation from AES surfactants is believed to occur at multiple points. The first point of dioxane generation in AES surfactants is during the sulfation process of alcohol ethoxylate to produce alcohol ethoxy sulfate. The alcohol ethoxylate intermediate for producing alcohol ethoxy sulfate surfactants is typically made through ethoxylation (i.e., reaction of alcohol with ethylene oxide), which results in a distribution of alcohol ethoxylate oligomers. It is believed that dioxane can be formed under the sulfation process conditions.

[0004] A second point of dioxane formation in AES surfactants is during handling and processing. Handling and processing of sulfated surfactants often involves acidic conditions at ambient or elevated temperatures. Prolonged exposure of AES surfactants and their alcohol ethoxylate precursors to acidic environments can result in the formation of dioxane. Furthermore, exposure to elevated temperatures during processing (e.g., 280°C), storage, and handling can result in the decomposition of AES surfactants, resulting in the formation of dioxane. Therefore, AES surfactants that exhibit thermal stability reduce the dioxane concentration in the product.

[0005] Traditionally, the dioxane content in sulfated surfactants and surfactant-incorporating products has been addressed by using stripping techniques. For example, when the dioxane concentration exceeds a target threshold, a stripping process is used to remove excess dioxane from the sulfated surfactant or surfactant-incorporating product. The stripping process is expensive and time-consuming. Furthermore, because dioxane can form over time depending on how the surfactant or product is handled and further processed, any previously applied stripping techniques can be rendered ineffective by the generation of new dioxane. Therefore, ensuring that products made from sulfated surfactants comply with appropriate regulations before being sold to the end consumer is a difficult task.

[0006] In view of the above, it is surprising and advantageous to discover alcohol ethoxylate and sulfated surfactants that resist forming greater than 9 ppm dioxane after both sulfation and exposure to elevated temperatures up to 280°C. Summary of the Invention

[0007] The inventors of the present application have discovered alcohol ethoxylate and sulfated surfactants that resist forming greater than 9 ppm dioxane after both sulfation and exposure to high temperatures up to 280°C.

[0008] The inventors of the present disclosure have discovered that the above-mentioned properties can be achieved with a surfactant composition in which 95 mole percent ("mol %) or more of the surfactants have a single ethylene oxide unit and 5 mole % or less of the surfactants have an ethylene oxide content of 2 or greater. Without being bound by theory, it is believed that the distribution of oligomers produced during alkoxylation is responsible for the formation of dioxane in both alcohol ethoxylates and sulfated surfactants. It is believed that oligomers having an ethylene oxide ("EO") number of 2 or greater may undergo a "back-biting" reaction to produce undesirable dioxane. Surprisingly, by limiting the presence of 2 EO unit oligomers to 5 mole % or less, the surfactant can resist the formation of 9 ppm of dioxane both during sulfation and when exposed to 280°C. Furthermore, it has been discovered that the above-mentioned alcohol ethoxylates can be produced by contacting an alcohol with an olefin in the presence of a metallosilicate catalyst.

[0009] The present invention is particularly useful in the formation of AES surfactants and products made therefrom.

[0010] According to a first aspect of the present disclosure, a process comprises contacting an olefin, an alcohol, and a metallosilicate catalyst to form an oligomer of alcohol ethoxylate having structure (I), wherein R1 is alkyl, R2 is alkyl, and n has a value of 1 to 3; and sulfating the oligomer of structure (I) to form an oligomer of structure (II), wherein R1 is alkyl, R2 is selected from the group consisting of alkyl groups, M is selected from the group consisting of protons, ammonium cations, metal cations, nitrogen cations, boron cations, phosphorus cations, triethylamine, triethanolamine, monoethanolamine, and combinations thereof, and n has a value of 1 to 3, wherein at least 95 mole percent of the oligomers of structure (II) have an n of 1 and no more than 5 mole percent of the oligomers of structure (II) have an n of 2 or greater.

[0011] According to a second feature of the present disclosure, the olefin is a C to C 18 The alcohol is monoethylene glycol.

[0012] According to a third feature of the present disclosure, the total number of carbon atoms in R1 and R2 is 7 to 17.

[0013] According to a fourth feature of the present disclosure, the total number of carbon atoms in R1 and R2 is 11 to 13.

[0014] According to a fifth aspect of the present disclosure, the catalyst for making structure (I) has a viscosity of 680 mPa s as measured according to ASTM D4365-19. 2 / g of surface area.

[0015] According to a sixth feature of the present disclosure, at least 98 mole percent of the oligomers of structure (I) have n equal to 1, and at most 2 mole percent of the oligomers of structure (I) have n equal to 2 or greater.

[0016] According to a seventh feature of the present disclosure, a surfactant composition comprises an oligomer of a surfactant having Structure (II), wherein R1 is alkyl, R2 is alkyl, M is selected from the group consisting of a proton, an ammonium cation, a metal cation, a nitrogen cation, a boron cation, a phosphorus cation, triethylamine, triethanolamine, monoethanolamine, and combinations thereof, and n has a value from 1 to 3, wherein 95 mole percent or more of the oligomers of Structure (II) in the composition have an n of 1, and 5 mole percent or less of the oligomers of Structure (II) in the composition have an n of 2 or greater.

[0017] According to an eighth feature of the present disclosure, R1 in structure (II) is a C1-C 16 alkyl, and R2 is C1-C 16 alkyl, and the total number of carbon atoms in R1 and R2 is 7 to 17.

[0018] According to a ninth feature of the present disclosure, at least 98 mole percent of the oligomers of Structure (II) in the surfactant composition have n of 1, and at most 2 mole percent of the oligomers of Structure (II) in the surfactant composition have n of 2 or greater.

[0019] According to a tenth feature of the present disclosure, the total number of carbon atoms in R1 and R2 is 11 to 13.

[0020] According to an eleventh feature of the present disclosure, the material comprises 0.1% to 99.9% by weight of a surfactant composition. DETAILED DESCRIPTION OF THE INVENTION

[0021] As used herein, the term "and / or," when used in a list of two or more items, means that any one of the listed items can be used by itself, or any combination of two or more of the listed items can be used. For example, if a composition is described as containing components A, B, and / or C, the composition can contain A alone, B alone, C alone, A and B in combination, A and C in combination, B and C in combination, or A, B, and C in combination.

[0022] Unless otherwise stated, all ranges are inclusive of the endpoints.

[0023] Test methods refer to the most current test method as of the priority date of this document unless the test method number indicates a date with a two-digit number with a hyphen. References to test methods include both a reference to the testing organization and the test method number. Test method organizations are referred to by one of the following abbreviations: ASTM refers to ASTM International (formerly known as the American Society for Testing and Materials), EN refers to European Norm, DIN refers to the Deutsches Institut fur Normung, and ISO refers to the International Organization for Standards.

[0024] IUPAC codes describing crystalline structures as drawn by the Structure Commission of the International Zeolite Association refer to their current designations as of the priority date of this document, unless otherwise specified.

[0025] As used herein, the term weight percent ("wt %") indicates that a component is a weight percent of the total weight of the indicated composition.

[0026] Alcohol Ethoxylate The present disclosure provides a compound having structure (I):

[0027] [ka] wherein R1 is alkyl, R2 is selected from the group consisting of alkyl groups, and n has a value of 1 to 3. The alkyl in R1 may have from 1 carbon atom (i.e., a C1 alkyl) to 16 carbon atoms (i.e., a C 16For example, R1 may be a C1 alkyl, or a C2 alkyl, or a C3 alkyl, or a C4 alkyl, or a C5 alkyl, or a C6 alkyl, or a C7 alkyl, or a C8 alkyl, or a C9 alkyl, or a C 10 Alkyl, or C 11 Alkyl, or C 12 Alkyl, or C 13 Alkyl, or C 14 Alkyl, or C 15 Alkyl, or C 16 The alkyl of R1 may be saturated or unsaturated. The alkyl of R2 may be C1 to C 16 For example, R2 may be a C1 alkyl, or a C2 alkyl, or a C3 alkyl, or a C4 alkyl, or a C5 alkyl, or a C6 alkyl, or a C7 alkyl, or a C8 alkyl, or a C9 alkyl, or a C 10 Alkyl, or C 11 Alkyl, or C 12 Alkyl, or C 13 Alkyl, or C 14 Alkyl, or C 15 Alkyl, or C 16 The alkyl in R2 may be saturated or unsaturated. The total number of carbon atoms present in R1 and R2 may be 7 to 17. For example, the total number of carbon atoms present in R1 and R2 may be 7 or more, or 8 or more, or 9 or more, or 10 or more, or 11 or more, or 12 or more, or 13 or more, or 14 or more, or 15 or more, or 16 or more, and at the same time, 17 or less, or 16 or less, or 15 or less, or 14 or less, or 13 or less, or 12 or less, or 11 or less, or 10 or less, or 9 or less, or 8 or less. n in structure (I) has a value of 1 to 3. For example, n may be 1, 2, or 3. The number of carbon atoms present in R1 and R2 and the value of n are all as provided below. 13 Determined according to C nuclear magnetic resonance characterization.

[0028] Due to the natural distribution of products resulting from the process used in forming the alcohol ethoxylates of structure (I), oligomers of structure (I) may have varying values ​​of n. For example, a composition of oligomers of structure (I) may have the same R1 and R2 but different n values ​​of 1, 2, and 3. Overall, 95 mole percent or more of the oligomers of structure (I) have an n of 1, and 5 mole percent or less of the oligomers of structure (I) have an n of 2 or greater. For example, 95.0 mol % or more, or 95.5 mol % or more, or 96.0 mol % or more, or 96.5 mol % or more, or 97.0 mol % or more, or 97.5 mol % or more, or 98.0 mol % or more, or 98.5 mol % or more, or 99.0 mol % or more, or 99.5 mol % or more, and simultaneously 100.0 mol % or less, or 99.5 mol % or less, or 99.0 mol % or less, or 98.5 mol % or less, or 98.0 mol % or less, or 97.5 mol % or less, or 97.0 mol % or less, or 96.5 mol % or less, or 96.0 mol % or less, or 95.5 mol % or less of the oligomers of structure (I) are provided below. 13 As determined according to C nuclear magnetic resonance characterization, the oligomers of structure (I) have an n value of 1. Additionally, 5.0 mol% or less, or 4.5 mol% or less, or 4.0 mol% or less, or 3.5 mol% or less, or 3.0 mol% or less, or 2.5 mol% or less, or 2.0 mol% or less, or 1.5 mol% or less, or 1.0 mol% or less, or 0.5 mol% or less, and simultaneously 0.0 mol% or more, or 0.5 mol% or more, or 1.0 mol% or more, or 1.5 mol% or more, or 2.0 mol% or more, or 2.5 mol% or more, or 3.0 mol% or more, or 3.5 mol% or more, or 4.0 mol% or more, or 4.5 mol% or more of the oligomers of structure (I) are provided below. 13 have an n value of 2 or greater, as determined according to C nuclear magnetic resonance characterization.

[0029] surfactant composition The present disclosure relates to a surfactant composition, the surfactant composition comprising a surfactant having the structure (II):

[0030] [ka] (wherein R1 is alkyl and R2 is alkyl), wherein the alkyl in R1 is C1 to C 16 For example, R1 may be a C1 alkyl, or a C2 alkyl, or a C3 alkyl, or a C4 alkyl, or a C5 alkyl, or a C6 alkyl, or a C7 alkyl, or a C8 alkyl, or a C9 alkyl, or a C 10 Alkyl, or C 11 Alkyl, or C 12 Alkyl, or C 13 Alkyl, or C 14 Alkyl, or C 15 Alkyl, or C 16 The alkyl of R1 may be saturated or unsaturated. The alkyl of R2 may be C1 to C 16 For example, R2 may be a C1 alkyl, or a C2 alkyl, or a C3 alkyl, or a C4 alkyl, or a C5 alkyl, or a C6 alkyl, or a C7 alkyl, or a C8 alkyl, or a C9 alkyl, or a C 10 Alkyl, or C 11 Alkyl, or C 12 Alkyl, or C 13 Alkyl, or C 14 Alkyl, or C 15 Alkyl, or C 16 The alkyl in R2 may be saturated or unsaturated. The total number of carbon atoms present in R1 and R2 may be 7 to 17. For example, the total number of carbon atoms present in R1 and R2 may be 7 or more, or 8 or more, or 9 or more, or 10 or more, or 11 or more, or 12 or more, or 13 or more, or 14 or more, or 15 or more, or 16 or more, and at the same time, 17 or less, or 16 or less, or 15 or less, or 14 or less, or 13 or less, or 12 or less, or 11 or less, or 10 or less, or 9 or less, or 8 or less. In certain examples, the total number of carbon atoms in R1 and R2 of structure (II) is 11 to 13. The value of n in structure (II) has a value of 1 to 3. For example, n may be 1, 2, or 3. The number of carbon atoms present in R1 and R2 and the value of n are all as provided below. 13Determined according to C nuclear magnetic resonance (“NMR”) characterization.

[0031] M in structure (II) is selected from the group consisting of a proton, an ammonium cation, a metal cation, a nitrogen cation, a boron cation, a phosphorus cation, triethylamine, triethanolamine, monoethanolamine, and combinations thereof. It will be understood that different surfactant molecules may have different materials for M.

[0032] Like structure (I), structure (II) can vary in the value of n, such that in the surfactant composition, 95 mole percent or more of the oligomers of structure (II) have an n of 1, and 5 mole percent or less of the oligomers of structure (II) have an n of 2 or greater. For example, 95.0 mol% or more, or 95.5 mol% or more, or 96.0 mol% or more, or 96.5 mol% or more, or 97.0 mol% or more, or 97.5 mol% or more, or 98.0 mol% or more, or 98.5 mol% or more, or 99.0 mol% or more, or 99.5 mol% or more, and at the same time 100.0 mol% or less, or 99.5 mol% or less, or 99.0 mol% or less, or 98.5 mol% or less, or 98.0 mol% or less, or 97.5 mol% or less, or 97.0 mol% or less, or 96.5 mol% or less, or 96.0 mol% or less, or 95.5 mol% or less of the oligomers of structure (II) in the composition have an n value of 1. Furthermore, 5.0 mol% or less, or 4.5 mol% or less, or 4.0 mol% or less, or 3.5 mol% or less, or 3.0 mol% or less, or 2.5 mol% or less, or 2.0 mol% or less, or 1.5 mol% or less, or 1.0 mol% or less, or 0.5 mol% or less, and simultaneously 0.0 mol% or more, or 0.5 mol% or more, or 1.0 mol% or more, or 1.5 mol% or more, or 2.0 mol% or more, or 2.5 mol% or more, or 3.0 mol% or more, or 3.5 mol% or more, or 4.0 mol% or more, or 4.5 mol% or more of the oligomers of Structure (II) in the composition have an n value of 2 or greater.

[0033] The surfactant composition may have a 1,4 dioxane content of 9 ppm or less, as measured according to the GCMS and LCMS methods described in more detail below. For example, the surfactant composition may exhibit 1,4 dioxane of 9 ppm or less, or 8 ppm or less, or 7 ppm or less, or 6 ppm or less, or 5 ppm or less, or 4 ppm or less, or 3 ppm or less, or 2 ppm or less, or 1 ppm or less. As explained above, the relative molar concentrations of the oligomers of structures (I) and (II) mean that dioxane formation is resisted not only during the sulfation process, but also in the presence of heat and over time.

[0034] material The present disclosure is also directed to materials comprising the surfactant composition. The materials may be personal care products, cleaning products, coatings, emulsion polymerization solutions, textile processing additives or compositions, agricultural adjuvants or compositions, oil and gas production additives or compositions, inks, paper and pulp additives or compositions, and other industrial process additives or compositions. The materials may comprise from 0.1 weight percent ("wt. %") to 99.9 wt. % of the surfactant composition, based on the total weight of the material. For example, the material may contain 0.1 wt% or more, or 1.0 wt% or more, or 5.0 wt% or more, or 10 wt% or more, or 20 wt% or more, or 30 wt% or more, or 40 wt% or more, or 50 wt% or more, or 60 wt% or more, or 70 wt% or more, or 80 wt% or more, or 90 wt% or more, or 99 wt% or more, and at the same time 99.9 wt% or less, or 99 wt% or less, or 90 wt% or less, or 80 wt% or less, or 70 wt% or less, or 60 wt% or less, or 50 wt% or less, or 40 wt% or less, or 30 wt% or less, or 20 wt% or less, or 10 wt% or less, or 5 wt% or less, or 1.0 wt% or less of the surfactant composition, based on the total weight of the material. As with the surfactant composition, the material may have a 1,4 dioxane content of 9 ppm or less, as measured by headspace gas chromatography using flame ionization detection, as described in more detail below.

[0035] process The present disclosure is also directed to a process comprising contacting an olefin, an alcohol, and a metallosilicate catalyst to form an oligomer of an alcohol ethoxylate having structure (I).

[0036] An alcohol ethoxylate having structure (I) is produced by contacting an olefin, an alcohol, a metallosilicate catalyst, and a solvent. The chemical reaction of the olefin and the alcohol is catalyzed by the metallosilicate catalyst in a reactor to produce the alcohol ethoxylate having structure (I).

[0037] The reaction of the olefin with the alcohol can occur at temperatures between 50°C and 300°C, or between 100°C and 200°C. In a specific example, the reaction can be carried out at 135°C. The reaction of the olefin with the alcohol can be carried out in a batch reactor, a continuous reactor, or a fluidized bed reactor. In the operation of the chemical reaction, the Bronsted acid sites of the metallosilicate catalyst catalyze the etherification of the olefin to the alcohol through an addition-type reaction. The reaction of the olefin with the alcohol produces an alcohol ethoxylate having the structure (I).

[0038] olefin The olefins used in the present process can be linear, branched, acyclic, cyclic, or mixtures thereof. The olefins range from C8 to C 18 The olefin may be a C8 olefin, a C9 olefin, or a C 10 Olefin, or C 11 Olefin, or C 12 Olefin, or C 13 Olefin, or C 14 Olefin, or C 15 Olefin, or C 16 Olefin, or C 17 Olefin, or C 18 It may also be an olefin.

[0039] The olefin may be an alpha (α) olefin, an internally disubstituted olefin, or a cyclic structure (e.g., C to C 12The olefin may include an alkene such as a cycloalkene. An alpha olefin includes an unsaturated bond at the alpha position of the olefin. Suitable alpha olefins may be selected from the group consisting of 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-icosene, 1-docosene, and combinations thereof. An internal disubstituted olefin includes an unsaturated bond that is not at the terminal position of the olefin. The internal olefin may be selected from the group consisting of 2-octene, 3-octene, 4-octene, 2-nonene, 3-nonene, 4-nonene, 2-decene, 3-decene, 4-decene, 5-decene, and combinations thereof. Other exemplary olefins may include butadiene and styrene.

[0040] Examples of suitable commercially available olefins include NEODENE™ 8, NEODENE™ 10, NEODENE™ 12, NEODENE™ 14, NEODENE™ 16, NEODENE™ 1214, NEODENE™ 1416, NEODENE™ 16148 manufactured by Shell (The Hague, Netherlands).

[0041] alcohol The alcohol used in the present process is an alkylene glycol. The alcohol may be selected from the group consisting of monoethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, monopropylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-propanediol, 1,2-butanediol, 2,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanemethanediol, glycerol, and / or combinations thereof. According to various examples, the alcohol is a (poly)alkylene glycol such as monoethylene glycol, diethylene glycol, propylene glycol, and triethylene glycol.

[0042] The molar ratio of alcohol to olefin in the present process can be 20:1 or less, or 15:1 or less, or 10:1 or less, or 9:1 or less, or 8:1 or less, or 7:1 or less, or 6:1 or less, or 5:1 or less, or 4:1 or less, or 3:1 or less, or 2:1 or less, or 0.2:1 or less, while simultaneously being 0.1:1 or more, or 1:1 or more, or 1:2 or more, or 1:3 or more, or 1:4 or more, or 1:5 or more, or 1:6 or more, or 1:7 or more, or 1:8 or more, or 1:9 or more, or 1:10 or more, or 1:15 or more, or 1:20 or more.

[0043] Metallosilicate Catalyst As used herein, the term "metallosilicate catalyst" refers to an aluminosilicate (commonly referred to as a zeolite) compound having a crystal lattice in which one or more metal elements are substituted for silicon atoms. The crystal lattice of the metallosilicate catalyst forms internal cavities and channels in which cations, water, and / or small molecules may reside. The substitute metal elements may include one or more metals selected from the group consisting of B, Al, Ga, In, Ge, Sn, P, As, Sb, Sc, Y, La, Ti, Zr, V, Cr, Mn, Pb, Pd, Pt, Au, Fe, Co, Ni, Cu, and Zn. The metallosilicate catalyst may be substantially free of Hf. According to various examples, the metallosilicate may have a silica-to-alumina ratio of 5:1 to 1,500:1, as measured using neutron activation analysis. The silica to alumina ratio can be from 5:1 to 1,500:1, or from 10:1 to 500:1, or from 10:1 to 400:1, or from 10:1 to 300:1, or from 10:1 to 200:1. Such silica to alumina ratios can be advantageous in providing a highly homogeneous metallosilicate catalyst with organophilic-hydrophobic selectivity for adsorbing non-polar organic molecules.

[0044] The metallosilicate catalyst may have one or more exchangeable cations outside the crystal lattice. The exchangeable cations may be H + , Li + , Na + , Rb + , Cs + , Mg2+ , Ca 2+ , Sr 2+ , Ba 2+ ,Sc. 3+ , Y 3+ , La 3+ , R4N + , R4P + (wherein R is H or alkyl).

[0045] Metallosilicate catalysts can have a variety of crystalline structures, including, for example, MFI (e.g., ZSM-5), MEL (e.g., ZSM-11), BEA (e.g., β-type zeolite), FAU (e.g., Y-type zeolite), MOR (e.g., mordenite), MTW (e.g., ZSM-12), and LTL (e.g., Linde L), when described using IUPAC codes according to the nomenclature of the International Zeolite Association's Structure Commission.

[0046] The crystalline framework of metallosilicate catalysts is represented by a network of molecular-sized channels and cages composed of corner-sharing tetrahedron [TO4] (T = Si or Al) primary building blocks. Negative charge can be introduced onto the framework through isomorphous substitution of tetravalent silicon atoms with trivalent metal (e.g., aluminum) atoms. Overall charge neutrality is then achieved by the introduction of cationic species that compensate for the resulting negative lattice charge. When such charge compensation is provided by protons, Brønsted acid sites are formed, making the resulting H-form of the zeolite a strong solid Brønsted acid.

[0047] The metallosilicate catalyst can be used in the present process in various forms, for example, the metallosilicate catalyst can be a powder (e.g., particles having a longest linear dimension of less than 100 micrometers), granular (e.g., particles having a longest linear dimension of 100 micrometers or more), or a shaped article of powder and / or granular metallosilicate catalyst.

[0048] The metallosilicate catalyst is 100m 2 / g or more, or 200m 2 / g or more, or 300m 2 / g or more, or 400m 2 / g or more, or 500m 2 / g or more, 600m 2 / g or more, or 700m 2 / g or more, or 800m 2 / g or more, or 900m 2 / g or more, while at the same time, 1000m 2 / g or less, or 900m 2 / g or less, or 800m 2 / g or less, or 700m 2 / g or less, or 600m 2 / g or less, or 500m 2 / g or less, or 400m 2 / g or less, or 300m 2 / g or less, or 200m 2 The surface area may be measured in accordance with ASTM D4365-19.

[0049] The metallosilicate catalyst can be synthesized by hydrothermal synthesis. For example, the metallosilicate catalyst can be synthesized by heating a composition containing a silica source (e.g., silica sol, silica gel, and alkoxysilane), a metal source (e.g., metal sulfate, metal oxide, metal halide, etc.), and a quaternary ammonium salt such as tetraethylammonium salt or tetrapropylammonium salt to a temperature of about 100°C to about 175°C until a crystalline solid is formed. The resulting crystalline solid is then filtered, washed with water, dried, and then calcined at a temperature of 350°C to 600°C.

[0050] Examples of suitable commercially available metallosilicate catalysts include CP814E, CP814C, CP811C-300, CBV712, CBV720, CBV760, CBV2314, CBV10A from ZEOLYST INTERNATIONAL™ of Conshohocken, PA.

[0051] Sulfation After formation of the oligomer of structure (I), a step of sulfating the oligomer of structure (I) to form an oligomer of structure (II) is carried out. Sulfation of the alcohol ethoxylate having structure (I) is achieved by contacting the alcohol ethoxylate with a sulfating agent capable of sulfating the alcohol using a known process described in the references (David W. Roberts, "Sulfonation Technologies for Anionic Surfactant Manufacture", Organic Process Research & Development 1998, 2, 194 - 202; Xavier Domingo, "Alcohol and Alcohol Ether Sulfates", in Anionic Surfactants (Organic Chemistry), Surfactant Science Series Vol. 56 (Helmut W. Stache, ed.), Marcel Dekker, Inc., New York, 1996). Useful sulfating agents include chlorosulfonic acid, sulfuric acid, sulfur trioxide, and sulfamic acid. When chlorosulfonic acid is used as the sulfating agent, the sulfation is carried out at a temperature of -10 °C to 10 °C and a pressure of 0.01 megapascals ("MPa") to 1 MPa. The sulfating agent may be metered into the alcohol ethoxylate or may be combined with the alcohol ethoxylate at once. Once the desired level of sulfation of the alcohol ethoxylate is reached, a base (e.g., NaOH, KOH, or NH4OH) can be used to neutralize the sulfate or sulfate-containing compound and terminate the sulfation reaction.

Example

[0052] Materials The catalyst is a metallosilicate catalyst defined by the BEA structure, having a silica to alumina ratio of 25:1 and a surface area of 680 m 2 / g, and is commercially available as CP814E manufactured by ZEOLYST INTERNATIONAL (trademark) of Conshohocken, PA.

[0053] 1-Dodecene is an alpha olefin commercially available as NEODENE™ 12 from the SHELL™ Group of The Hague, Netherlands.

[0054] 1-Tetradecene is an alpha olefin commercially available as NEODENE™ 14 from the SHELL™ Group of The Hague, Netherlands.

[0055] Monoethylene glycol is liquid anhydrous ethylene glycol purchased from SIGMA ALDRICH™ having CAS number 107-21-1.

[0056] ALEO1 is commercially available from Huntsman Corporation, The Woodlands, Texas, under the trade name SURFONIC™ L24-1. 13 It is a linear primary alcohol ethoxylate having an average of one ethylene oxide unit as determined by C NMR characterization.

[0057] ALEO2 is a linear primary C copolymer commercially available under the trade name BIOSOFT™ N25-7 from Stepan Company, Northfield, Illinois. 12 ~C 15 It is an ethoxylate of 7 moles of alcohol.

[0058] Sulfuric acid is an ACS reagent (95-98%) from SIGMA ALDRICH™ with a CAS number of 7664-93-9.

[0059] Chlorosulfonic acid is a liquid purchased from SIGMA ALDRICH™ having a CAS number of 7790-94-5.

[0060] Sodium hydroxide (NaOH) is a solid purchased from SIGMA ALDRICH™ having a CAS number of 1310-73-2.

[0061] Dichloromethane (DCM) is liquid anhydrous dichloromethane purchased from SIGMA ALDRICH™ having CAS number 75-09-2.

[0062] SA3EO sulfate is C 12 It is a secondary alcohol ethoxylate having three ethylene oxide units, sulfated in the same manner as described below for EO Sulfate. The base starting material is C 2 O 4 O 5 O 6 ... 12 ~C 14 A secondary alcohol ethoxylate, which is commercially available as TERGITOL™ 15-S-3 from The Dow Chemical Company, Midland, Michigan.

[0063] Dioctyl Sodium Sulfosuccinate (SDOSS) BioXtra ≧99.0% is a solid having CAS number 577-11-7 purchased from SIGMA ALDRICH™.

[0064] Sodium dodecyl sulfate (SDS) ≥ 99.0% (GC) dust-free pellets were purchased from SIGMA ALDRICH™ and have the CAS number 151-21-3.

[0065] Hyamine 1622 (benzethonium chloride) ≥ 99.0% (AT) is a solid having CAS number 121-54-0 purchased from SIGMA ALDRICH™.

[0066] Methylene Blue (Certified Biological Stain) is a solid with CAS number 7220-79-3 purchased from Fischer Scientific™.

[0067] Anhydrous sodium sulfate (Granular / Certified ACS) is a solid having CAS number 7757-82-6 purchased from Fischer Scientific™.

[0068] Test Method Method for determining percent active sulfate content This procedure is a modification of Turney, M.E., Cannell, D.W. "Alkaline methylene blue method for determination of anionic surfactants and for amine oxides in detergents." J. Am. Chem. Soc., 42, 544-546 (1965) and Epton, S.R.A. "New method for the rapid titrimetric analysis of sodium alkyl sulfates and related compounds." Trans. Faraday Soc., 44, 226-230 (1948). 1. Dioctyl Sodium Sulfosuccinate (SDOSS), Control Solution - A 20 mL scintillation vial was charged with 0.8 g (±0.1 mg) of dioctyl sodium sulfosuccinate of known purity (≥99%). The vial was filled with 10 mL of DI water and transferred to a 250 mL volumetric flask. This process was repeated 3-5 times to ensure sample transfer. Once the transfer was complete, the sample was diluted with DI water to the mark (250 mL). The flask was then stoppered and the solution was thoroughly mixed by repeatedly inverting the flask. To verify accuracy, a second control solution can be made with sodium dodecyl sulfate (SDS) of purity ≥ 99% using the same procedure as above. If a second control solution is used, be sure to adjust Equation 1 accordingly. b. Purity of the control sample should be >99%. The formula listed below does not take purity into account, so if the control sample is lower than this, it must be taken into account. 2. Methylene Blue Chloride Solution - A 20 mL scintillation vial was charged with 0.050 g (±0.005) of methylene blue chloride. The vial was filled with 10 mL of DI water and transferred to a 1 L graduated cylinder. This process was repeated 3-5 times to ensure accurate sample transfer. The methylene blue solution was then diluted to the 1 L mark. This solution was then transferred to a 2 L glass container. Once the transfer was complete, 10 mL of concentrated sulfuric acid and 50 g of anhydrous sodium sulfate were carefully added to the methylene blue solution and mixed thoroughly. 3. Hyamine 1622 Solution - A 20 mL scintillation vial was charged with 1.1 grams of Hyamine 1622. The vial was filled with 10 mL of DI water and transferred to a 1 L volumetric flask. This process was repeated 3-5 times to ensure accurate sample transfer. The sample was then diluted to the 1 L mark with DI water. The solution was thoroughly mixed by repeatedly inverting the flask and then filtered into a 1 L glass bottle. 4. Standardization of Hyamine Solution - 5 mL of dioctyl sodium sulfosuccinate solution was pipetted into a 100 mL glass bottle. Next, 20 mL of methylene blue chloride solution and 25 mL of chloroform were pipetted. The 100 mL bottle was capped and vigorously shaken for several seconds. The Hyamine 1622 solution was then titrated into the methylene blue / chloroform biphasic mixture in 0.5 mL increments. After each addition, the bottle was capped and vigorously shaken. Addition of Hyamine 1622 continued in 0.5 mL increments until the blue color of the chloroform layer (or bottom layer) began to migrate to the top layer. At this point, the addition of Hyamine 1622 was reduced to 0.1 mL and continued until the endpoint was reached. The endpoint was reached when the blue intensity of both layers was consistent. This standardization was completed in triplicate. The moles of Hyamine 1622 were calculated using the following formula:

[0069]

number

[0070]

number

[0071] Acid Digestion Procedure 0.5 g of the alcohol ethoxylate material to be tested is placed in a sample vial. Concentrated sulfuric acid (4.0 grams, 95-98% ACS reagent) is then added to form a reaction solution, and the sample vial is tightly capped. The sample vial is then placed on a heating block and the sample is heated to 90 °C. Once the set temperature is reached, the reaction is allowed to react for 1 hour. Once complete, the reaction sample vial is removed and cooled to 23 °C. While the sample is cooling, 0.9 grams of 1 molar aqueous NaOH solution is placed in a separate gas chromatography headspace vial and cooled in an ice bath. After the reaction solution has cooled, 0.1 grams is added to the pre-cooled gas chromatography headspace vial. The vial is immediately capped and returned to the ice bath. The sample is then analyzed by headspace gas chromatography with flame ionization detection ("HS-GC / FID") to determine the amount of 1,4-dioxane formed during digestion. Because 1,4-dioxane forms a complex with sulfuric acid, a neutralization step is necessary to liberate the 1,4-dioxane produced during sulfuric acid digestion of the sample.

[0072] Acid digestion analysis The neutralized headspace vial is heated to 90°C for 15 minutes to allow the concentration of 1,4-dioxane to equilibrate in the headspace. A 2.5 mL aliquot of the headspace is extracted using a gas-tight syringe heated to 150°C and then injected into a gas chromatography instrument. The volatile components in the headspace sample are separated using a Porabond Q column and then detected by flame ionization detection. The Porabond Q column is used because it does not readily decompose under acidic or basic conditions and can provide the best separation and detection limit for 1,4-dioxane among other acid-digested sample matrix components. Quantitation is performed by external standardization; the method has been found to have a detection limit of 0.1 ppm (w / w) for 1,4-dioxane.

[0073] [Table 1]

[0074] Liquid injection cryogenic GCMS of organic layers Standards were prepared by adding dioxane to tetrahydrofuran ("THF") and diluting from 0.1 to 100 ppm.

[0075] Samples were prepared by combining 3.3 g of the organic (DCM) layer of the crude process mixture with 6.7 g of THF, then shaking the solution for approximately 20 minutes. The solids were then centrifuged to the bottom, and the supernatant was placed in an autosampler vial. Spiked samples were prepared by adding dioxane standards in THF to separate samples at 5-10 ppm.

[0076] LCMS of the aqueous layer

[0077] [Table 2]

[0078] Samples were injected neat or diluted 1:4 with water. Standards were prepared by preparing a dioxane in THF stock solution and diluting with water to 0.1-100 ppm.

[0079] Calculation of dioxane content for solids The ppm of dioxane content relative to the solid content in the sample is calculated according to Equation 3.

[0080]

number

[0081] Calculating EO content The weight percent ethylene oxide content in the sample was calculated according to Equation 2, where MW is the molecular weight in g / mol.

[0082]

number

[0083] Nuclear Magnetic Resonance ("NMR") Characterization for EO Distribution Samples dissolved in deuterated dimethyl sulfoxide containing 0.025 M chromium(III) acetylacetonate 13 C NMR spectra are collected on a Bruker AVANCE 400 MHz spectrometer equipped with a 10 mm cryoprobe set at 25°C. Spectra are acquired with the following parameters: 90° pulse, inverse gate decoupling, 1.38 s acquisition time, and 6.4 s recycle delay. 2048 scans were collected. Data are processed with MNOVA, and chemical shifts are referenced to the solvent peak at 39.52 ppm. DEPT-135 experiments are also acquired with the same parameters except for a 2.0 s recycle delay and 2048 scans.

[0084] The ratio of the different EO adducts is calculated by integrating and comparing the intensities of the ethylene oxide alcohol end group at about 60-61 ppm, the ethylene oxide backbone group at about 69-70 ppm, the ethylene oxide end group ether peak at about 71-72 ppm, the unreacted primary alcohol peak at about 60-61 ppm, and the unreacted secondary alcohol peak at about 65-66 ppm.

[0085] Sample preparation C 12 Synthesis of EO A 3-liter ("L"), three-necked, glass, round-bottom flask equipped with a centrally stirred overhead, a reflux condenser, and a heating jacket was used for the catalytic etherification of 1-dodecene and monoethylene glycol. A pitch-blade impeller was used for stirring to ensure good mixing. A reaction mixture of 551.7 grams ("g") of ethylene glycol and 505.8 g of 1-dodecene was prepared and charged to the reactor at 23°C along with 61 g of catalyst in powder form. The impeller stirring speed was set at 400 revolutions per minute ("rpm"). The reactor was heated to 135°C over 30 minutes, held at 135°C for 18 hours, and then cooled to 23°C by turning off the heater. A separatory funnel was used to separate the reaction mixture into a monoethylene glycol and catalyst phase and an olefin phase.

[0086] The distillation apparatus was configured using a 1-liter round-bottom flask connected to a short-path distillation head with a thermometer adapter and a condenser with a vacuum adapter at the outlet. The distillation flask was heated in an aluminum block by an IKA heated stir plate. The combined olefin phases were placed in the distillation pot, and stirring and vacuum were then applied. Significant boiling was observed, but no condensate was observed or collected. The temperature of the heating block was increased to 75°C, and unreacted dodecane was collected at distillation head temperatures of 25°C to 50°C and pressures of 13.3 to 40 Pascals ("Pa"). The heating block temperature was gradually increased to 140°C, and an intermediate fraction containing both monoether alcohol ethoxylate and dodecene was collected while the head temperature was increased from 50°C to 75°C at a pressure of 13 Pa. 12EO was collected at head temperatures between 70°C and 115°C and pressures between 6 Pa and 33 Pa. The heating block temperature was gradually increased to 200°C, and the head temperature was increased from 115°C to 130°C at a pressure of 6 Pa while collecting intermediate fractions containing both monoether alcohol ethoxylates and diethers. The distillation was stopped, and the diethers remaining in the pot were collected. To understand the product composition, C 12 The EO samples were characterized by NMR, which is reported in the Results section. 12 The EO was then subjected to a sulfation process to produce sulfate anionic surfactants.

[0087] C 12 Preparation of EO sulfate and ALEO1 sulfate All chemical manipulations were carried out under a dry nitrogen atmosphere. Prior to the experiments, all glassware was heated in a laboratory oven to remove residual water. A 2 L three-necked round-bottom flask was charged with dichloromethane (500 mL) and C 12 EO (40 g, 0.173 mol, 1.0 equiv.) was charged. The reaction flask was equipped with an overhead mechanical stirrer, an addition funnel, and a thermocouple. Next, chlorosulfonic acid (12.7 mL, 0.191 mol, 1.1 equiv.) was carefully added to the addition funnel. The reaction flask was then immersed in an ice bath and cooled to 0 °C for 20 minutes. Once the reaction was cooled, chlorosulfonic acid was added dropwise to the reaction flask at a rate of approximately 1.0 mL / min over a period of approximately 20 minutes. The reaction temperature did not exceed 5 °C during the addition of the chlorosulfonic acid. After the addition, the reaction was allowed to react, maintaining the temperature between 0 and 5 °C for 3 hours. At this point, the reaction was neutralized by the slow, dropwise addition of aqueous NaOH (18.0 g NaOH, 0.9 mol, in 500 mL water). The addition rate was slow enough that it did not exceed 5 °C over the course of the addition. The solution became basic after the addition of approximately 300 mL of 0.9 M NaOH solution. The dichloromethane was then carefully removed from the two-phase reaction mixture in vacuo. During the removal of the dichloromethane, a large amount of foaming was observed. After the dichloromethane was removed, the remaining aqueous solution was placed in a freeze dryer / lyophilizer to obtain the secondary alcohol ethoxylate sulfate product, C. 12EO sulfate was obtained as a white solid (61.9 grams). The secondary alcohol ethoxylate sulfate product was 79.9% active by weight as measured according to the method for determining percent active sulfate content.

[0088] The synthesis of ALEO1 sulfate and SA3EO sulfate was carried out by C 12 The same procedure was followed as for EO sulfate.

[0089] C 14 Synthesis of EO For the catalytic etherification of 1-tetradecene and monoethylene glycol, a 300 mL Parr reactor equipped with a heating jacket and control devices was used. A pitched blade impeller was used for agitation to ensure good mixing.

[0090] A reaction mixture of 100.0 g of monoethylene glycol and 100.0 g of 1-tetradecene was prepared and charged to a reactor at 23°C along with 10.0 g of powdered catalyst. The impeller agitation speed was set to at least 600 rpm. The reactor was heated to 135°C in 30 minutes, held at 135°C for 6 hours, and then cooled to room temperature by turning off the heater. The reaction mixture was separated using a separatory funnel. Using the separatory funnel, the reaction mixture was separated into a monoethylene glycol and catalyst phase and an olefin phase. Fifteen batches were produced, and the olefin phase was collected and combined for distillation.

[0091] C 12 The same distillation apparatus used in the synthesis of EO was used as C 14This was used for the distillation of EO. The olefin phase product from multiple batch reactor runs was placed in a distillation pot, which was then stirred and vacuum applied. Significant boiling was observed, but no condensate was observed or collected. The heating block temperature was increased to 95°C, and unreacted 1-tetradecene was collected at a distillation head temperature of 30°C to 60°C and a pressure of 27 Pa to 5 Pa. The heating block temperature was gradually increased to 170°C, and an intermediate fraction containing both the monoether and tetradecene was collected as the head temperature increased from 60°C to 85°C at a pressure of 7 Pa to 5 Pa. 14 EO was collected at a head temperature of 80°C to 115°C and a pressure of 8 Pa to 5 Pa. Distillation was stopped when no more material was distilling with the pot temperature set at 170°C. 14 The EO samples were characterized by NMR.

[0092] C 14 Preparation of EO sulfate All chemical manipulations were carried out under a dry nitrogen atmosphere. Prior to the experiments, all glassware was heated in a laboratory oven to remove residual water. A 2 L three-necked round-bottom flask was charged with dichloromethane (500 mL) and C 14EO (50 g, 0.193 mol, 1.0 equiv.) was charged. The reaction flask was equipped with an overhead mechanical stirrer, an addition funnel, and a thermocouple. Next, chlorosulfonic acid (14.2 mL, 0.213 mol, 1.1 equiv.) was carefully added to the addition funnel. The reaction flask was then immersed in an ice bath and cooled to 0 °C for 20 minutes. Once the reaction was cooled, chlorosulfonic acid was added dropwise to the reaction flask at a rate of approximately 1.0 mL / min over a period of approximately 20 minutes. The reaction temperature did not exceed 5 °C during the addition of the chlorosulfonic acid. After the addition, the reaction was allowed to react, maintaining the temperature between 0 and 5 °C for 3 hours. At this point, the reaction was neutralized by the slow, dropwise addition of aqueous NaOH (18.0 g, 0.9 mol in 500 mL of water). The addition rate was slow enough that it did not exceed 5 °C over the course of the addition. The solution became basic after the addition of approximately 400 mL of 0.9 M NaOH solution. The dichloromethane was then carefully removed from the two-phase reaction mixture in vacuo. During the removal of the DCM, a large amount of foaming was observed. After the DCM was removed, the remaining aqueous solution was placed in a freeze dryer / lyophilizer to yield the secondary alcohol ethoxylate sulfate product (68.6 grams). The secondary alcohol ethoxylate sulfate product was 87.9 wt% active.

[0093] General procedure for carrying out and measuring the dioxane content formed during sulfation Similar conditions were used to prepare the C12EO and C14EO sulfate materials. A 2 L, three-necked, round-bottom flask was charged with 400–500 mL of dichloromethane and 35–50 grams (1 equivalent) of the alcohol ethoxylate to be tested. The reaction flask was equipped with an overhead mechanical stirrer, an addition funnel, and a thermocouple. Next, chlorosulfonic acid (1.1 equivalents) was carefully added to the addition funnel. The reaction flask was then immersed in an ice bath and cooled to 0°C for 20 minutes. Once the reaction was cooled, chlorosulfonic acid was added dropwise to the reaction flask at a rate of approximately 1.0 mL / min over a period of approximately 20 minutes. The reaction temperature did not exceed 5°C during the addition of the chlorosulfonic acid. After the addition, the reaction was allowed to react, maintaining the temperature at 0–5°C for 3 hours. At this point, the reaction was neutralized by the slow dropwise addition of aqueous NaOH (18.0 g, 0.9 M in 500 mL of water). The rate of addition was slow enough that it did not exceed 5°C over the course of the addition. Once neutralized, the biphasic mixture was analyzed by GC to determine the dioxane content formed during sulfation. The crude sample was tightly sealed and stored in a refrigerator until analytical analysis was performed.

[0094] result Alcohol Ethoxylate The results of the NMR tests are shown in Table 1 below.

[0095] [Table 3]

[0096] As expected, C. 12 EO and C 14 At least 95 mole percent of the oligomers of structure (I) in EO have n=1, and C 12 EO and C 14 Not more than 5 mole percent of the oligomers of structure (I) in EO have n equal to or greater than 2. Specifically, C 12 EO and C 14 At least 98 mole percent of the oligomers of structure (I) in EO have n=1, and C 12 EO and C 14Not more than 2 mole percent of the oligomers of structure (I) in EO have n of 2 or greater.

[0097] Table 2 shows the results of the acid digestion tests for the comparative examples ("CE") and the inventive examples ("IE").

[0098] [Table 4]

[0099] Given the above understanding of how dioxane is thought to form, it is important to understand the stability of alcohol ethoxylates in acidic environments, such as H2SO4 acid digestion experiments. CE1 demonstrates that alcohol ethoxylates with an EO content of 2 or greater readily produce dioxane under conditions such as acid digestion tests. Under acidic conditions, 2.53 wt% (25,300 ppm) of dioxane was observed, with 37% of the EO converted to 1,4-dioxane.

[0100] Although CE2 had an average of 1 EO, CE2 contained significant amounts of unreacted alcohol and 2EO adducts (i.e., 0 EO and ≥ 2 EO, but less than 1 EO). As explained above, alcohol ethoxylates with ≥ 2 EO provide a chemical route for forming 1,4-dioxane under acidic conditions. Therefore, it is not surprising that CE2 exhibited 0.35 wt% (3500 ppm) dioxane and 16% EO conversion to 1,4-dioxane. Therefore, ALEO1 and ALEO2 of CE1 and CE2 clearly face issues regarding dioxane regulations if used in products and exposed to sulfur-containing acidic compounds.

[0101] C as IE1 12EO was also tested in the acid digestion study. After acid digestion, the 1,4-dioxane content was 0.00052 wt % (5.2 ppm), confirming that compositions rich in 1EO alcohol ethoxylate (i.e., ≥ 95 mol %) exhibit better stability under acidic conditions, thereby preventing 1,4-dioxane formation. A very small amount of 1,4-dioxane was observed in IE1, likely due to 1 mol % of 2EO or higher oligomers of structure (I). C 14 EO is expected to provide the same low dioxane concentration since it also has a single EO unit.

[0102] Sulfated surfactants Table 3 shows the dioxane measurements for sulfated surfactants.

[0103] [Table 5] a = Dioxane was not detected up to the limit of 0.1 ppm b = Dioxane concentration calculated from the average concentration in the aqueous and organic phases at 110°C. c = Dioxane concentration relative to the solid was calculated based on the average concentration d = calculated based on the detection limit of (0.1) ppm

[0104] Gas chromatography results for CE3 showed that the secondary alcohol 3EO sulfate contained 15.3 ppm dioxane relative to the solid and 2.0 ppm dioxane in the organic phase at 110 °C, indicating the problem of two or more EO units potentially generating dioxane. Interestingly, when the inlet temperature was increased to 280 °C, the dioxane content of the secondary alcohol 3EO sulfate increased significantly from 2 ppm to 1471 ppm. This result indicates that sulfated surfactants with two or more EO units can generate observable dioxane at 110 °C, but also indicates that such surfactants may not be stable at temperatures as high as 280 °C, resulting in significant dioxane formation. Similar to CE3, gas chromatography results for CE4 (i.e., sulfated ALEO1) indicate the formation of unacceptable amounts of dioxane relative to the solid (i.e., >9 ppm). Furthermore, CE4 also showed significant dioxane generation (259 ppm) at 280 °C, suggesting that CE4 is not stable at high temperatures. IE3 exhibits low dioxane content due to 95 mole % or more of 1EO oligomers and 5 mole % or less of 2EO or higher oligomers. Surprisingly, IE3 also exhibits extremely low dioxane content, below the limit of detection (LOD) of the GC and LC methods. Using the LOD as a reference, this indicates that the dioxane content of IE3 is less than 1.6 ppm based on the solid at 110°C. Interestingly, even when the inlet temperature is increased to 280°C, the dioxane content of the IE3 material is still less than 1.0 ppm (0.58 ppm). This is indicative of the C 12 It shows that EO can not only prevent dioxane formation in the sulfation process, but also has increased thermal stability to resist dioxane formation compared to the comparative examples.

Claims

1. contacting an olefin, an alcohol, and a metallosilicate catalyst to form a compound of structure (I) 【Chemical 1】 (In the formula, R １ is alkyl, and R ２ is alkyl and n has a value of 1 to 3; The oligomer of structure (I) is sulfated to form an oligomer of structure (II) 【Chemistry 2】 (In the formula, R １ is alkyl, and R ２ is selected from the group consisting of alkyl groups; M is selected from the group consisting of protons, ammonium cations, metal cations, nitrogen cations, boron cations, phosphorus cations, triethylamine, triethanolamine, monoethanolamine, and combinations thereof; and n has a value from 1 to 3; The method wherein 95 mole percent or more of said oligomers of structure (II) have n equal to 1 and 5 mole percent or less of said oligomers of structure (II) have n equal to 2 or greater.

2. The olefin is ８ ~C １８ 2. The method of claim 1, wherein the alcohol is an alpha olefin and the alcohol is monoethylene glycol.

3. R １ and R ２ The method according to claim 1 or 2, wherein the total number of carbon atoms in the alkylene oxide is 7 to 17.

4. R １ and R ２ The method of claim 3, wherein the total number of carbon atoms in the alkyl group is 11 to 13.

5. The catalyst for making structure (I) has a viscosity of 680 ml as measured according to ASTM D4365-19. ２ The method according to any one of claims 1 to 4, wherein the surface area of ​​the SiO2 nanoparticles is 1 / g.

6. 6. The method of any one of claims 1 to 5, wherein 98 mole percent or more of the oligomers of structure (I) have n of 1 and 2 mole percent or less of the oligomers of structure (I) have n of 2 or greater.

7. Structure (II) 【Chemistry 3】 (In the formula, R １ is alkyl, and R ２ is alkyl; M is selected from the group consisting of a proton, an ammonium cation, a metal cation, a nitrogen cation, a boron cation, a phosphorus cation, triethylamine, triethanolamine, monoethanolamine, and combinations thereof; and n has a value from 1 to 3; a surfactant composition wherein 95 mole percent or more of the oligomers of structure (II) in said composition have n of 1, and 5 mole percent or less of the oligomers of structure (II) in said composition have n of 2 or greater.

8. R in structure (II) １ But C １ ~C １７ alkyl, and R ２ But C １ ~C １６ alkyl, and further comprising R １ and R ２ 8. The surfactant composition according to claim 7, wherein the total number of carbon atoms in is 7 to 17.

9. 9. The surfactant composition of Claim 7 or 8, wherein 98 mole percent or more of said oligomers of Structure (II) in said surfactant composition have n of 1 and 2 mole percent or less of said oligomers of Structure (II) in said surfactant composition have n of 2 or greater.

10. R １ and R ２ 8. The surfactant composition according to claim 7, wherein the total number of carbon atoms in is 11 to 13.

11. A material comprising 0.1% to 99.9% by weight of the surfactant composition of claim 7.

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