[0001] The present technology relates to esterquat compositions that employ esterquat actives derived from biorenewable sources. In particular, the present technology relates to esterquat actives that have a Biorenewable Carbon Index (BCI) of 100. The esterquat compositions are particularly useful in fabric softening applications.

BACKGROUND OF THE INVENTION

[0002] Recently there has been a trend to formulate products with ingredients that are based on renewable resources derived from plants or animals, rather than fossil fuels. Such ingredients are considered “green” or “natural”, since they are derived from renewable and/or sustainable sources. As a result, they are more environmentally friendly than ingredients derived from fossil fuels. An ingredient having a high Biorenewable Carbon Index (BCI), such as greater than 80, indicates that the ingredient contains carbons that are derived primarily from plant, animal or marine-based sources. There has also been an increased interest in more environmentally sustainable and eco- friendly products. Products with a higher concentration of active ingredients and less water are desirable since they typically require less packaging, and therefore have a smaller environmental impact due to, for example, reduced transportation costs and less waste production.

[0003] Esterquat quaternary ammonium compounds (esterquats) have been used as fabric softening actives for many years. Such esterquats are typically made from fatty acids reacted with an amine, such as triethanolamine (TEA) or methyl diethanolamine (MDEA) and then quaternized. Although the fatty acids used to make esterquats are derived from plants or animals, which are biorenewable sources, TEA and MDEA are derived from nonrenewable, petroleum sources. Thus, esterquats are only partially derived from biorenewable sources.

[0004] Esterquats are also usually in a solid or paste form, and require heating/melting or dilution with a solvent, such as IPA or ethanol, which could release volatile organic compounds (VOCs) into the environment. Moreover, formulating such compounds into concentrated liquid compositions can result in products that may not be stable upon storage, especially when stored at high temperatures or at freezing temperatures. Instability can manifest itself as thickening of the product upon storage, even to the point that the product is no longer pourable.

[0005] Another problem with concentrated esterquat compositions is that they typically require a solvent in order to have a product that has a low enough viscosity in its molten state that it is able to be pumped with conventional equipment. The added solvent is usually a volatile organic compound (VOC), such as isopropanol or ethanol, which is undesirable from an environmental standpoint. Moreover, stricter regulations limiting VOCs have been proposed, making it important to limit or eliminate solvents that contribute VOCs.

[0006] There is a need in the art for a fabric softening active that is derived primarily or entirely from biorenewable sources and can deliver fabric softening properties comparable to traditional esterquat fabric softening actives. It would also be an advantage if the fabric softening active could provide a highly concentrated fabric softener system that does not require a VOC solvent, and can remain stable in concentrated form during storage.

SUMMARY OF THE INVENTION

[0007] One aspect of the present technology is directed to a fabric softening composition comprising (a) an esterquat fabric softening active that is the reaction product of (i) glycine betaine reacted with (ii) one or more Guerbet alcohols having a total carbon content of 24 to 28 carbon atoms, and (iii) ethanesulfonic acid; and (b) solvent or liquid carrier to total 100% of the composition, wherein the fabric softening active has a BCI of at least 95.

[0008] In a further aspect, the present technology is directed to a concentrated fabric softening composition comprising (a) an esterquat fabric softening active that is the reaction product of (i) glycine betaine reacted with (ii) one or more Guerbet alcohols having a total carbon content of 24 to 28 carbon atoms, and (iii) ethanesulfonic acid; and (b) solvent to total 100% of the composition, wherein the fabric softening active comprises from greater than 50 wt% to about 90 wt% of the fabric softening composition.

[0009] Another aspect of the present technology is a method of making a fabric softening active, wherein one or more Guerbet alcohols having from 24 to 28 total carbons atoms is reacted with glycine betaine in the presence of ethanesulfonic acid in a ratio of one molar equivalent of glycine betaine to 1 .0 to 1 .5 molar equivalents of Guerbet alcohol and 1.1 to 1 .2 molar equivalents of ethanesulfonic acid, in the absence of added solvent, to form a reaction product comprising a compound having the following chemical structure:

CH ₃ CH ₂ SO ₃ - wherein R + R’ totals 22 to 26 carbon atoms. Alternatively, more specifically,

or mixtures thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

[0010] [not applicable]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] While the present technology will be described in connection with one or more preferred embodiments, it will be understood by those skilled in the art that the technology is not limited to only those particular embodiments. To the contrary, the presently described technology includes all alternatives, modifications, and equivalents as may be included within the spirit and scope of the appended claims.

[0012] “Biorenewable Carbon Index” (BCI) refers to a calculation of the percent carbon derived from a biorenewable resource, and is calculated based on the number of biorenewable carbons divided by the total number of carbons in the entire molecule.

[0013] “Biorenewable” is defined herein as originating from animal, plant, or marine material. [0014] “VOC” refers to volatile organic compounds. Such compounds have a vapor pressure of greater than 2 mm Hg at 25°C, less than 7 carbon atoms, and a boiling point at atmospheric pressure of less than 120°C.

[0015] The term “fabric softening active” means a compound that has a fabric softening or conditioning property.

[0016] The term “fabric softening composition” means a composition comprising a fabric softening active.

[0017] The term “concentrated fabric softening composition” means a composition comprising a fabric softener active in an amount of about 50 wt% or greater.

Glycine Betaine Esterquats

[0018] The fabric softening compositions of the present technology comprise, as a fabric softening active, an esterquat material that is the esterification reaction product of glycine betaine reacted with a Guerbet alcohol in the presence of ethanesulfonic acid. Glycine betaine is a bioderived quaternary ammonium amino acid that is the by-product produced during the production of sugar from beet root. It has a trimethyl alkyl quaternary ammonium group and a carboxylate functional group. Glycine betaine has a BCI of 100 since it is derived from a biorenewable source, and is considered generally regarded as safe (GRAS).

[0019] Guerbet alcohols are f3-alkylated dimer fatty alcohols produced by the high temperature self-condensation of fatty alcohols. The resulting dimerized alcohols have two hydrophobic “tails” (hydrocarbon chains) due to branching, and also have lower melting points than the straight chain alcohols from which they are derived. Using fatty alcohols derived from biorenewable sources in the Guerbet dimerization process results in a Guerbet alcohol having a BCI of 100. Bioderived Guerbet alcohols are commercially available with differing amounts of total carbons, up to 32 total carbons. One source for Guerbet alcohols is Sasol, North America under the name Isofol. The preferred Guerbet alcohols used in the esterification reaction with glycine betaine have the following chemical structure: wherein R + R’ totals 22 to 26 carbon atoms. The carbon chain lengths are in the range of 10 to 14 carbon atoms, and total carbon atoms are in the range of 24 to 28 total carbon atoms. Guerbet alcohols having a total carbon atom amount of greater than 28 carbons may be too hydrophobic for use in a fabric softening composition, and Guerbet alcohols having 20 or less total carbon atoms may provide inferior softening properties compared to conventional esterquat fabric softeners.

[0020] The glycine betaine esterquats of the present technology are prepared by reacting glycine betaine with one or more Guerbet alcohols in the presence of ethanesulfonic acid. Since ethanesulfonic acid can also be derived from biorenewable sources, the resulting glycine betaine esterquat can be derived entirely from biorenewable sources to provide a fabric softening active having a BCI of at least 95, preferably a BCI of 100. In one process for preparing glycine betaine esterquat, 1 molar equivalent of glycine betaine is reacted with 2 to 3 molar equivalents of ethanesulfonic acid and 1 to 1.5 molar equivalents of Guerbet alcohol (high acid process) according to the following reaction scheme:

[0021 ] Surprisingly, the reaction can take place at a reaction temperature in the range of 100 °C to 130 °C without added solvent. Typically, higher temperatures, such as 150 °C or more, and/or added solvent are used to drive the esterification reaction to completion. Without being bound by theory, the branching structure of the Guerbet alcohol may make the esterification reaction more favorable, such that higher temperatures or added solvent are not necessary to facilitate the reaction.

[0022] The resulting esterification reaction product comprises a mixture of compounds in which at least 60% by weight is glycine betaine esterquat having the following chemical structure:

CH ₃ CH ₂ SO ₃ -

[0023] The remainder of the mixture is comprised of unreacted Guerbet alcohol and ethanesulfonic acid, and can also include minor amounts of etherified Guerbet alcohol, ethanesulfonic salt of unreacted glycine betaine, and sulfonate ester of Guerbet alcohol. Because a substantial excess of ethanesulfonic acid is used to drive the esterification reaction to completion, the unreacted ethanesulfonic acid can comprise about 18 wt% or more of the reaction product mixture (high acid reaction product). The reaction product mixture can be used in the present technology without purification or separation of the glycine betaine esterquat.

[0024] The glycine betaine esterquats resulting from using a large molar excess of ethanesulfonic acid do not form the conventional low-active (i.e. 5 wt% to 15 wt%) aqueous dispersions used in fabric softening compositions. Without being bound by theory, it is believed that the large excess of ethanesulfonic acid in the reaction product mixture can form high salt concentrations that prevent the high acid esterquat reaction product from forming stable esterquat aqueous dispersions upon dilution. Instead, the high acid glycine betaine esterquat reaction product can form a stable concentrated system comprising about 50 wt% of the reaction product up to about 90 wt% based on the total weight of the concentrated system. Alternatively, the high acid reaction product can comprise about 55 wt% to about 85 wt%, alternatively about 60 wt% to about 85 wt%, alternatively about 65 wt% to about 80 wt% by weight, alternatively about 65 wt% to about 75 wt% of the concentrated system. The stable concentrated system also includes from about 10 wt% to about 50 wt% of one or more selected solvents described further herein.

[0025] The glycine betaine esterquats of the present technology can also be prepared by an alternative, low-acid process in which 1.1 to 1 .2 molar equivalents of ethanesulfonic acid, rather than 2 to 3 molar equivalents, are used in the esterification reaction (low acid process). Surprisingly, even without a substantial excess of ethanesulfonic acid, the reaction can take place at a reaction temperature in the range of 100 °C to 140 °C without added solvent. [0026] The resulting reaction product (low acid reaction product), like the high acid reaction product, also comprises a mixture of compounds, but the composition of the mixture is different and has different properties than the high acid reaction product. The low acid reaction product comprises a higher amount of glycine betaine esterquat, at least 65 wt%, and a lower amount, less than 5 wt%, of unreacted ethanesulfonic acid. The glycine betaine esterquat from the low acid process can be formulated into low-active (e.g. 5 wt% to 15 wt%) stable aqueous dispersions, but are not able to form stable concentrated fabric softener systems.

Concentrated Fabric Softening Compositions

[0027] The glycine betaine esterquat reaction product resulting from the high acid esterification process can form a stable concentrated fabric softening composition when combined with one or more particular solvents. The one or more solvents can comprise from about 10 wt% to about 50 wt%, alternatively about 15 wt% to about 45 wt%, alternatively about 15 wt% to about 40 wt%, alternatively about 20 wt% to about 35 wt%, alternatively about 25 wt% to about 35 wt%, based on the weight of the concentrated fabric softener system. The solvent system used herein has a low VOC content, or is free of VOCs, and comprises solvents that are derived wholly or primarily from biorenewable sources. Conventional solvents used in fabric softening compositions, such as ethanol, propanol, and butanol, are not desirable for use in the fabric softening compositions of the present technology, since they are VOC solvents and are derived from petroleum sources. Preferably, only non-VOC solvents derived from biorenewable sources are used in the composition so that the solvent system has a BCI of at least 85, and the fabric softening composition has an overall BCI of at least 90. [0028] Solvents that can be used in the solvent system include polyethylene glycols, fatty amides, 1 ,3-dialkoxy-2-propanols, or combinations thereof. Polyethylene glycols that can be used are those having a number average molecular weight in the range of 130 to 700, alternatively 170 to 400, alternatively 190 to 300, alternatively 195 to 210. Number average molecular weight can be determined by methods known in the art, such as size exclusion chromatography. One example of a suitable polyethylene glycol (PEG) solvent is PEG 200 (also known as PEG-4), having a number average molecular weight of about 200. PEG 200 is not a VOC solvent, and is available in 100% plant-based form from Acme-Hardesty. When derived from a 100% plant-based source, PEG 200 has a BCI of 100.

[0029] The fatty amides that can be used in the solvent system have the following general structure: wherein R is branched or straight, saturated or unsaturated alkyl or alkenyl having from 6 to 20, preferably 8 to 14 carbon atoms, or combinations thereof. In some embodiments, R can contain one or more hydroxyl groups. R1 and R2 are independently hydrogen, a C1 to C6 alkyl group, or a C2 to C6 alkenyl group, optionally containing one or more hydroxyl groups and can optionally be branched when 3 or more carbon atoms are present, or mixtures thereof. Examples of feedstocks which can be used to make the alkyl amides include lauric fatty acid, myristyl fatty acid, coconut fatty acid, soy fatty acid and ricinoleic fatty acid, or the corresponding methyl esters of these feeds. Specific examples of R1 and R2 groups include methyl, ethyl, and 2-propanol. Commercial examples of dialkyl amides include, but are not limited to, di-isopropyl amides available under the tradename COLA® Liquid from Colonial Chemical, Inc., and dimethyl amides commercially available from Stepan Company under the tradenames NINOL® and Hallcomid®. One example of a suitable alkyl amide is NINOL®CAA, a mixture of dimethyl lauramide and dimethyl myristamide (CAA) available from Stepan Company. CAA is derived primarily from renewable sources, has a BCI of 86, and is a non-VOC solvent. Other examples of suitable alkyl amides available from Stepan Company are HALLCOMID® M-10 (N, N-dimethylcapramide; M-10) and HALLCOMID® M-8-10 (mixture of N,N-dimethylcaprylamide N, N-dimethylcapramide; M-8-10); all the carbons in these molecules, except for the methyl groups on the nitrogen, are from plant sources. Another example is STEPOSOL® MET-1 OU (N, N-dimethyl 9-decenamide; MET-1 OU) - MET-1 OU is also available from Stepan Company.

[0030] The 1 ,3-dialkoxy-2-propanols that can be used in the solvent system have the following general structure: wherein Ra and Rb are independently a C1 to C6 alkyl group, or a C2 to C6 alkenyl group, optionally containing one or more hydroxyl groups, and can optionally be branched when 3 or more carbon atoms are present, or mixtures thereof. One example of a suitable 1 ,3- dialkoxy-2-propanol solvent is 1 ,3-diethoxy-2-propanol (DEP). DEP is not a VOC solvent, and can be prepared by synthetic routes that utilize biorenewable feedstocks rather than petroleum based feedstocks. When derived from biorenewable feedstocks, DEP has a

BCl of 100.

[0031] The solvents in the solvent system are selected so that the concentrated fabric softening compositions are clear, chemically stable, and storage stable. In some embodiments, a clear, stable, concentrated composition can be obtained with a solvent system that comprises a single solvent. In other embodiments, it may be necessary to use a mixture of particular solvents in order to obtain the desired stability. A concentrated fabric softening composition comprising a 1 ,3-dialkyl-2-propanol as the only solvent has been found to be stable. The 1 ,3-dialkyl-2-propanol solvent could also be combined with one or more of the other solvents recited above to form the solvent system. It has also been found that a solvent system comprising a mixture of at least one polyethylene glycol and at least one fatty amide, as defined above, can provide clear, stable, concentrated liquid compositions. The weight ratio of polyethylene glycol to fatty amide in the solvent system can range from 1 :3 to 3: 1 , alternatively 1 :2 to 2: 1 . In one embodiment, the solvent system comprises a mixture of PEG 200 and M-10.

[0032] The viscosity of the concentrated liquid fabric softening compositions is less than 5000 cP at 25°C, preferably less than 3000 cP at 25°C, and most preferably less than 1000 cP at 25°C.

Low-Active Fabric Softening Compositions

[0033] Glycine betaine Guerbet alcohol esterquats prepared by the low-acid process can be diluted in a liquid carrier to form a stable, aqueous dispersion comprising about 2 wt% to about 25 wt%, alternatively about 3 wt% to about 12 wt% of the glycine betaine low-acid reaction product, based on the total weight of the dispersion. Water is a preferred liquid carrier due to its low cost, relative availability, safety, and environmental compatibility. The low-active compositions are prepared by melting the esterquat at 70°C until it is a homogeneous liquid and separately heating the required amount of water to 75°C. The esterquat is then slowly added to the water over 5 minutes at a mixing speed of at least 500 RPM. The composition is then mixed for at least another 30 minutes before removing heat.

Optional Additional Ingredients

[0034] It is contemplated that the fabric softening compositions can optionally comprise additional ingredients as desired or needed. Additional ingredients include, but are not limited to, nonionic surfactants, cationic surfactants, amphoteric surfactants, imidazolines, mercaptans, glycerides, glycerin, silicones, such as polydimethyl siloxane, amino silicones, or ethoxylated silicones, cationic polymers, or any combination thereof. Such additional ingredients can range from 0 to about 30 wt%, based on the weight of the composition.

Adjunct ingredients

[0035] Adjunct ingredients may be added to the fabric softening compositions of the present technology. The term "adjunct ingredient" includes: dispersing agents, stabilizers, pH control agents, antifoaming agents, metal ion control agents, colorants, brighteners, dyes, odor control agent, pro-perfumes, cyclodextrin, perfume, solvents, soil release agents, preservatives, antimicrobial agents, chlorine scavengers, anti-shrinkage agents, fabric crisping agents, spotting agents, anti-oxidants, anti-corrosion agents, bodying agents, drape and form control agents, smoothness agents, static control agents, wrinkle control agents, sanitization agents, disinfecting agents, germ control agents, mold control agents, mildew control agents, antiviral agents, drying agents, stain resistance agents, malodor control agents, fabric refreshing agents, chlorine bleach odor control agents, dye fixatives, dye transfer inhibitors, color maintenance agents, color restoration and rejuvenation agents, anti-fading agents, whiteness enhancers, anti-abrasion agents, wear resistance agents, fabric integrity agents, anti-wear agents, rinse aids, UV protection agents, sun fade inhibitors, insect repellents, anti-allergenic agents, enzymes, flame retardants, water proofing agents, fabric comfort agents, water conditioning agents, stretch resistance agents, hydrate inhibitors, scale inhibitors, demulsifiers, oxygen scavengers, and combinations thereof. The adjunct ingredients may be added to the solid compositions in an amount of 0 to about 3% by weight of the composition.

Product Use

[0036] The fabric softening compositions of the present technology are suitable for use in the rinse cycle of a laundry process, in particular the rinse cycle of a home or industrial automatic laundry washing machine, or a hand washing laundry basin. For example, the fabric softening composition (either concentrated or dilute) can be dispensed from a fabric softener dispenser that is integral to the automatic laundry washing machine at the appropriate time during the laundry process. The concentrated composition can be added directly, without dilution, for example through a dispenser drawer or, for a top-loading washing machine, directly into the drum.

[0037] The amount of fabric softening composition added to the machine can be an amount sufficient to deliver about 1.5 g to about 8 g of esterquat active per wash load for concentrated formulations and about 20 g to about 40 g for dilute formulations. Such an amount typically provides about 0.04% to about 0.3 wt% glycine betaine esterquat active to the fabric, based on the weight of the dry fabric. For example, in order to deliver 0.15 wt% of the active esterquat on dry fabric (WOF), the dosage of a 50 wt% active esterquat formula for a 6 pound (2721.55 g) load of dry laundry is 8.16 g: (0.15%WOF)(2721 .55 g)/50% = 8.16 g, where WOF stands for weight on dry fabric. The 0.15% WOF is based on a commercial premium fabric softener dosage for a medium sized load per bottle instructions.

[0038] In some embodiments, the concentrated fabric softening composition can be dispensed as a fabric softening article, such as, but not limited to, a pod, a packet, a pouch, or a capsule. The fabric softening article has a water-soluble or water-rupturable coating or film that encapsulates or contains a unit dose of the concentrated fabric softening composition. The term “unit dose” as used herein refers to a pre-metered amount of fabric softening composition that should be delivered to a laundry solution to provide an effective amount of softening to a minimum amount of laundry articles in a minimum volume of laundry solution. For larger loads of laundry articles, multiple doses may be required for an effective amount of softening. Water-soluble or water-rupturable coatings or films are known in the art. Suitable materials for the coating or film include, but are not limited to, polyvinyl alcohol, polyvinyl pyrrolidone, methylcellulose, hydroxymethyl cellulose, partially hydrolyzed vinyl acetate, gelatins, and combinations thereof.

EXAMPLES

[0039] The presently described technology and its advantages will be better understood by reference to the following examples. These examples are provided to describe specific embodiments of the present technology. By providing these examples, the inventors do not limit the scope and spirit of the present technology.

[0040] The following test methods are used to determine properties of the glycine betaine Guerbet alcohol esterquats of the present technology. ¹ H NMR was performed on a JEOL 500 MHz spectrophotometer using CDCIs as solvent unless indicated otherwise. Melting point by DSC, total acidity, AV and amine value, percent moisture, and viscosity measurements were performed using standardized methods.

Example 1

[0041] Ethanesulfonic acid solution (70%, 178.03 g, 2.6 equiv.) was charged to a 1 L, 4-necked round-bottomed flask equipped with a mechanical stirrer, a thermocouple, and a short-path distillation apparatus. With stirring at ~200 rpm, 51 .1 g of glycine betaine was added in portions. An exotherm was noticed, and the temperature increased from 22.1 °C to a final temperature of 50.9°C. The heating mantle was installed, and the reaction temperature was held at 50°C. At this point, 251.51 g (OHV = 117.03 mg KOH/g, EW = 479.4 g/mol, 1.2 equiv.) of molten (80°C) Isofol® 32 was added using a weight-by- difference method. The slightly hazy acid solution remained a hazy mixture, but no solids formed, and the viscosity increased but remained stirrable. The reactor was placed under a 300 mL/min nitrogen headspace purge, and the contents were heated to 120°C and held for 1 hour. The temperature was then increased to 130°C and held for 1.75 hours. The receiver was then chilled in dry ice, and 25 mmHg was carefully applied to the system to aid the removal of moisture. After 2 hours under vacuum, the reaction mixture appears to have become homogeneous, and the cooling water was turned off due to solid formation in the condenser. The reaction was stirred at 130°C and 25 mmHg for a total of 7 hours, after which ¹ H NMR shows no further consumption of alcohol. The contents of the reactor were transferred to a 1 -quart French square sample jar.

[0042] A total of 413.20 g of product was transferred. % moisture = 0.13%; m.p. (DSC) = 15°C. Product composition ( ¹ H NMR): unreacted Isofol® 32 = 11.59%; ethanesulfonic acid = 18.49%; Glycine Betaine Ethanyl Sulfonate = 2.20%; Isofol® 32 Ester of Glycine Betaine Ethanyl Sulfonate = 63.02%. The Isofol® 32 Dialkyl Ether content could not be determined by ¹ H NMR.

Example 2

[0043] Ethanesulfonic acid solution (70%, 295.0 g, 2.6 equiv.) was weighed into a 1 L, 4-necked round-bottomed flask equipped with a mechanical stirrer, a thermocouple, and a short-path distillation apparatus vented to a mineral oil filled bubbler. A tared 500 mL round-bottomed flask was installed as the receiver. The reactor was seated in a heating mantle. A nitrogen source was attached to the remaining neck and the system was placed under a light nitrogen headspace purge and allowed to stir for 10 minutes. While stirring, 85.05 g (1 equiv.) of glycine betaine was added in two equal portions, allowing the exotherm to stop between additions. After the first addition, the temperature rose from 23.5°C to 36.0°C. After the second addition, the temperature rose from 35.5°C to 42.7°C. The mixture was stirred for 5 minutes, and then heated to 50°C. Once at 50°C, molten Isofol® 28 (mp = 27-33°C), 365.60 g (OHV = 134.39 mg KOH/g sample, EW = 417.44 g/mol, 1.2 equiv.), was added as quickly as possible. The heterogeneous mixture was then heated to 110°C at 300 rpm while under a 300 mL/min nitrogen headspace purge and held for 3 hours. The reaction mixture was then heated to 120°C and held for 3.25 hours. The temperature was increased to 130°C and held for 35.5 hours while periodically monitoring the disappearance of alcohol by ¹ H NMR. The reaction was stopped once the alcohol conversion reached 89.5%. The contents of the reactor were transferred to a tared, 1 -quart French square sample jar at 80°C.

[0044] A total of 637.13 g of product was transferred. Over the course of the reaction a total of 68.37 g of condensate (~68% of theoretical) was collected in the distillation receiver. % moisture = 0.01 %; total acidity = 1.854 meq/g; m.p. (DSC) = -8.1 °C. Product composition ( ¹ H NMR): Isofol® 28 = 11.25%; Dialkyl ether of Isofol® 28 = 1.76%; ethanesulfonic acid = 20.94%; Glycine Betaine Ethanyl Sulfonate = 3.48%; Isofol® 28 Ester of Glycine Betaine Ethanyl Sulfonate = 62.56%.

Example 3

[0045] Ethanesulfonic acid solution (70%, 295.02 g, 2.6 equiv.) was weighed into a 1 L, 4-necked round-bottomed flask and then equipped with a mechanical stirrer, a thermocouple, and a short-path distillation apparatus vented to a mineral oil filled bubbler. A tared 500 ml_ round-bottomed flask was installed as the receiver. The reactor was seated in a heating mantle. A nitrogen source was attached to the remaining neck and the system was placed under a light nitrogen headspace, and 85 g (1 equiv.) of glycine betaine was added in two equal portions, allowing the exotherm to stop before making the final addition. After the first addition, the temperature rose from 23.5°C to 36.8°C. After the second addition, the temperature rose from 36.3°C to 43.4°C. The mixture was stirred for 5 minutes, and then heated to 50°C. Once at 50°C, Isofol® 24 (314.67 g, OHV = 155.23 mg KOH/g sample, 1.2 equiv.) was added as quickly as possible. The heterogeneous mixture was then heated to 100°C at 300 rpm while under a 300 mL/min nitrogen headspace purge and held for 45 minutes. The reaction mixture was then heated to 120°C and held for 2 hours. At this point, the reaction mixture had become homogeneous. The reaction mixture was then heated to 130°C and held for 32.75 hours at which point ¹ H NMR indicated an alcohol percent conversion of 88.5%. A total of 78.9 g of condensate had collected in the receiver over the course of the reaction. The contents of the reactor were transferred at 80°C to a tared, 1 -quart French square sample jar.

[0046] A total of 590.0 g of product was transferred. Total acidity = 2.2742 meq/g; % moisture = 0.206%; melting point (DSC) = -46.5°C. Product composition ( ¹ H NMR): Isofol® 24 = 7.76%; Dialkyl ether of Isofol® 24 = 2.33%; ethanesulfonic acid = 23.39%; Glycine Betaine Ethanyl Sulfonate = 3.25%; Isofol® 24 Ester of Glycine Betaine Ethanyl Sulfonate = 63.09%; other ethanesulfonic acid species = 0.18%.

Example 4

[0047] Ethanesulfonic acid solution (70%, 346.84 g, 2.6 equiv.) was charged to a 4- necked, 2 L round-bottomed flask equipped with a mechanical stirrer, a thermocouple, and a short-path distillation apparatus vented to a mineral oil filled bubbler. A tared 500 mL pear shaped flask was attached to the short path as the receiver. With stirring, 99.98 g (1 equiv.) of glycine betaine was added in two equal portions, allowing the exotherm to subside after the first addition before adding the second portion. After the first addition (50.14 g), the internal temperature increased from 22.7°C to 34.1 °C, and after the second addition (49.85 g), the temperature increased from 34.0°C to 40.9°C. The solution was then thermostatted to 40°C and stirred for 15 minutes under a 300 mL/min nitrogen headspace sweep of nitrogen. Isofol® 20 (308.89 g, OHV = 186 mg KOH/g sample, EW = 301 .6 g/mol, 1 .2 equiv.) was then added under a nitrogen purge as quickly as possible by removing the short-path and adding the alcohol. Once the addition was complete, the reaction mixture was heated to 100°C and held for 45 minutes. The reaction mixture was then heated to 120°C and held for 2 hours. The reaction was then heated to 130°C and held for a total of 21.75 hours, after which ¹ H NMR indicates alcohol conversion to be 86.5%. A total of 99.86 g of condensate had collected in the receiver over the course of the reaction. The clear, homogeneous liquid was transferred from the reactor to a fared, 1 -quart French square sample jar.

[0048] A total of 620.25 g of product was transferred, m.p. (DSC) = <-60°C: total acidity = 2.1819 meq/g; AV and amine salts = 2.3499 meq/g; % moisture = 2721 ppm. Product composition ( ¹ H NMR): Isofol® 20 = 6.26%; Dialkyl Ether of Isofol 20 = 1.01 %; Ethanesulfonic acid = 24.67%; Glycine Betaine Ethanyl Sulfonate = 0.61 %; Isofol® 20 Ester of Glycine Betaine Ethanyl Sulfonate = 67.45%.

Example 5

[0049] Ethanesulfonic acid solution (70%, 348.0 g, 2.6 equiv.) was charged to a 4- necked, 2 L round-bottomed flask equipped with a mechanical stirrer, a thermocouple, and a short-path distillation apparatus vented to a mineral oil filled bubbler. A tared 500 mL pear shaped flask was attached to the short path as the receiver. With stirring, 100 g (1 equiv.) of glycine betaine was added in two equal portions, allowing the exotherm to subside after the first addition before adding the second portion. After the first addition (50.11 g), the internal temperature increased from 21 ,3°C to 33.6°C, and after the second addition (49.89 g), the temperature increased from 32.5°C to 39.8°C. The solution was then thermostatted to 40°C and stirred for 15 minutes under a 300 mL/min nitrogen headspace sweep of nitrogen. Isofol® 16 (251 .15 g, OHV = 230 mg KOH/g sample, EW = 243.91 g/mol, 1 .2 equiv.) was then added under a nitrogen purge as quickly as possible by removing the short-path and adding the alcohol. Once the addition was complete, the reaction mixture was heated to 110°C and held for 30 minutes. Once the temperature had reached 100°C, the reaction mixture appeared to be homogeneous. The reaction mixture was then heated to 120°C and held for 2 hours and became hazy during this time period. The reaction was then heated to 130°C and held for 19.5 hours while monitoring the disappearance of alcohol periodically. Alcohol consumption plateaued at 88%. A total of 109.43 g of condensate had collected in the receiver over the course of the reaction. The contents of the reactor were transferred to a fared, 1 -quart French square samplejar.

[0050] A total of 548.75 g of material was transferred. % moisture = 734 ppm; m.p. (DSC) = -74°C; AV and amine salts = 1 .7521 meq/g; total acidity = 2.5775 meq/g. Product composition ( ¹ H NMR): Isofol® 16 = 5.43%; Dialkyl Ether of Isofol® 16 = 0.98%; Ethanesulfonic Acid = 27.52%; Isofol® 16 Ester of Glycine Betaine Ethanyl Sulfonate = 64.17%.

Example 6

[0051] Ethanesulfonic acid solution (70%, 146.04 g, 1.1 equiv.) was charged to a 4- necked, 2 L round-bottomed flask equipped with a mechanical stirrer, a thermocouple, and a short-path distillation apparatus vented to a mineral oil filled bubbler. A tared 250 mL round-bottomed flask was attached to the short path as the receiver. The reactor was seated in a heating mantle. A nitrogen source was attached to the remaining neck and the system was placed under a light nitrogen headspace purge. With stirring, 100 g (1 equiv.) of glycine betaine was added in three equal portions, allowing the exotherm to subside after each addition before adding the next portion. Over the course of the betaine addition, the temperature rose from 23.5°C to 46.4°C (23.5 to 39.3°C; 39.2 to 45.6°C; 44.6 to 46.4°C). Once the addition was complete, 13.37 g of deionized water was used to rinse the solids funnel and the side of the reactor into the reaction mixture. The solution was then thermostatted to 50°C and stirred for 30 minutes under a 100 mL/min nitrogen headspace sweep of nitrogen. Isofol® 24 (363.32 g, OHV = 157 mg KOH/g sample, EW = 357.32 g/mol, 1 .2 equiv.) was then added under a nitrogen purge as quickly as possible by removing the short-path and adding the alcohol. Once the addition was complete, the reaction mixture was heated to 100°C and held for 30 minutes under a 400 mL/min nitrogen headspace sweep. The reaction mixture was then heated to 120°C and held for 1.5 hours and became hazy during this time period. The reaction was then gradually heated to a final temperature of 140°C as follows: 130°C and held for 8 hours, 135°C and held for 14.25 hours, and then 140°C and held for 29 hours while periodically monitoring the production of alcohol by ¹ H NMR. Ester formation plateaued at 76.2% (adjusted for excess alcohol). A total of 49.07 g of condensate had collected in the receiver over the course of the reaction. The reaction mixture was allowed to cool to 90°C, and the contents of the reactor were transferred to a tared, 1 -quart French square samplejar.

[0052] A total of 435.80 g of product was transferred. % moisture = 106 ppm; AV and amine salts = 0.5262 meq/g; total acidity = 1.7142 meq/g. Product composition ( ¹ H NMR): Isofol® 24 = 20.95%; Dialkyl Ether of Isofol® 24 = not detected; Ethanesulfonic Acid = 2.38%; Glycine Betaine Ethyl Sulfonate = 6.14%; Isofol® 24 Ester of Glycine Betaine Ethanyl Sulfonate = 70.53%.

Example 7

[0053] 70% aqueous ethanesulfonic acid solution (434.4 g) was charged to a 2 L, 4- necked round-bottomed flask equipped with a thermocouple, a mechanical stirrer, and a short-path distillation apparatus vented to a mineral oil filled bubbler. A fared 500 mL round-bottomed flask was installed on the short-path as a distillation receiver. Glycine betaine (125.02 g) was added in three approximately equal portions, allowing the exotherm to subside after each addition. The total temperature change over the course of the addition was from 21 ,0°C to 40.5°C. Once all of the glycine betaine had been added, the system was placed under a 300 mL/min nitrogen headspace sweep, and heated to 70°C. Once at 70°C, molten brassicyl alcohol (80°C, 382.59 g) was added as quickly as possible, and the mixture was then heated to 110°C and held for 45 minutes. The temperature was then increased to 120°C and held for 2 hours. The reaction mixture became homogeneous within minutes of reaching 120°C. The reaction mixture was then heated to 130°C and held for 30.5 hours while monitoring the disappearance of brassicyl alcohol by ¹ H NMR. Alcohol conversion reached 95.3% after 30.5 hours of reaction at 130°C, and a total of 78.32 g of condensate had collected in the distillation receiver over the course of the reaction. A 466.05 g portion of the reaction mixture was transferred at 80°C to a tared, 1 quart French square. The material had the following composition as determined by ¹ H NMR: unreacted Brassicyl alcohol = 2.57%; Dibrassicyl ether = 16.19%; Ethanesulfonic acid = 24.90%; other Ethanesulfonic acid species = 1.61 %; Glycine Betaine Ethanyl Sulfonate = 11.92%; Brassicyl Glycine Betaine Ethanyl Sulfonate = 42.81 %. % moisture = 2118 ppm; total acidity = 2.9272 meq/g sample; AV and amine salts = 2.7351 meq/g; melting point (DSC) = 65°C.

[0054] NEUTRALIZATION: In a separate 1 L, 4-necked reactor was transferred the remaining 301.60 g of the reaction mixture (A total of 767.65 g of product were split between the sample jar and the 1 L reactor). The reactor was then equipped with a mechanical stirrer, a short-path distillation apparatus, a thermocouple, and a nitrogen source. The system was placed under a light nitrogen headspace sweep and heated to 80°C.

[0055] Based on the compositional analysis, 301 .60 g of product contains 24.90 wt% free ethanesulfonic acid or 301.60 (0.2490) = 75.10 g of free ethanesulfonic acid. This equates to 75.10 g/110.132 g/moL = 0.682 moles of ethanesulfonic acid. In order to maintain an acidic pH of the product, 95% of the excess ethanesulfonic acid is to be neutralized due to literature reports showing that neutral or basic solutions of glycine betaines hydrolyze readily. Thus, 95% of 0.682 moles = 0.6478 moles of ethanesulfonic acid need to be neutralized, and 0.6478 moles of 50% caustic = 0.6478 moles (39.997 g/mol) = 25.91 g NaOH/O.51 = 50.80 g of 51 % aqueous NaOH solution (Fisher Scientific lot#: 188236) is to be used.

[0056] With stirring at 250 rpm, a 100 mL pressure equalized dropping funnel containing 50.81 g of caustic solution was attached to the reactor, and the nitrogen source was attached to the top of the funnel. With stirring, and under a 300 mL/min nitrogen headspace sweep, the caustic solution was added dropwise. The addition had to be stopped several times in order to allow the exotherm to subside, keeping the temperature below 90°C. After ~75% of the caustic solution had been added, the system began to gel, forming a gel layer on the sides of the reactor wall with a mixable, gelatinous material in the center. At this point, the reaction temperature was increased to 90°C. Once at 90°C, the remaining caustic solution was added slowly to the gelatinous reaction mixture. Once the addition was complete, the temperature was slowly increased to 120°C in 5°C increments, holding at each temperature for 10-15 minutes. The reaction mixture thinned and became more fluid and stirrable. Once at 120°C, the reaction mixture was stirred for 60 minutes at which point the reaction mixture had become the consistency of oatmeal. The reaction mixture was then cooled to room temperature and allowed to stand overnight under a light nitrogen headspace sweep. A total of 7.39 g of condensate had collected in the receiver.

[0057] The glycine betaine Guerbet alcohol esterquats prepared in Examples 1 -6 are clear, colorless to light yellow liquids that darken over time. Melting points range from 15 °C for the Example 1 esterquat to -74 °C for the Example 5 esterquat. The compositional analysis for each of the reaction products from Examples 1 -6 is provided in Table 1 , where the amounts are in wt% as determined by ¹ H NMR.

Table 1 : Compositional Analysis

“Salt” = ethanesulfonic acid salt of unreacted glycine betaine. “Other” = sulfonate ester of

Guerbet alcohol. “Acid” = ethanesulfonic acid. ND = not detected. Example 8

[0058] An attempt was made to form conventional low-active (5%) aqueous fabric softener dispersions by combining the esterquat reaction products prepared in Examples 1 -5 and 7 with water. None of the esterquats were able to form stable, low-active aqueous dispersions. The esterquat reaction products for Examples 1 -5 and 7 were then assessed to determine whether the esterquats could form stable concentrated systems. The esterquat reaction products prepared in Examples 1-5 were combined with a solvent system to form a concentrate comprising 70 wt% esterquat and 30 wt% solvent. The solvent systems used were either a combination of 15 wt% polyethylene glycol having a number average molecular weight of about 200 (PEG-200) and 15 wt% N,N- dimethylcapramide (Halcomid M-10, available from Stepan Company), or 30 wt% 1 ,3- diethoxy-2-propanol (DEP). The PEG200/M-10 solvent system has a BCI of 97.5, and the DEP solvent has a BCI of 100. The Example 7 esterquat reaction product was combined with water to form an aqueous concentrate comprising about 10 wt% esterquat and water to total 100%. The liquid fabric softener concentrates are shown in Table 2, where the ingredient amounts are in wt%.

Table 2: Concentrated Fabric Softening Compositions

[0059] The esterquat prepared from the C32 Guerbet alcohol (Example 1 ) did not form stable concentrates when formulated at 70 wt% esterquat and 30 wt% solvent with either solvent system. The brassicyl glycine betaine esterquat (Example 7) did not form stable aqueous dispersions. Surprisingly, the esterquats prepared in Examples 2-5 could be formulated into stable concentrated systems comprising 70% esterquat and 30% solvent. The esterquat prepared from the C28 Guerbet alcohol (Example 2) formed a stable 70 wt% concentrate with 30 wt% of the DEP solvent system, and the esterquats prepared from the C24, C20, and C16 Guerbet alcohols (Examples 3-5) formed stable concentrates when formulated with either solvent system. The fabric softening concentrates formulated with 30 wt% DEP as the solvent have an overall BCI of 100. The fabric softening concentrates formulated with 30 wt% of the PEG-200/M-10 solvent system having an overall BCI of greater than 95. The stable concentrates were all clear liquids with viscosities of less than 1000 cP at 25 °C.

Example 9

[0060] This example evaluates the softening ability of the stable esterquat systems from Example 8 compared to a conventional esterquat dispersion. Softening tests were run using the following methodology based on ASTM D-5237: white hand towels made from an 86/14 cotton/polyester blend were first subjected to a prewash process to remove any factory finish. For each test, 160 towels were washed in conventional household washing machines. Fabric softener samples were dosed into the machines during the rinse cycle. Towels were then tumble dried and allowed to equilibrate to room temperature overnight. Panelists then blindly evaluated pairs of towels via a Paired Comparison panel test. The number of votes were tallied for each sample. Using the One-Sided Directional Difference Test (Meilgaard, M.C., Civille, G.V., Carr, B.T., Sensory Evaluation Techniques, 3rd Ed., CRC Press, 1999, pp. 277-278, 355, 371 ), in a 160-vote observation test one product would need to be chosen a minimum of 91 times to be deemed statistically superior to the other at the 95% confidence level.

[0061] Using this test method, the concentrated fabric softening compositions from Example 8 were evaluated for softening performance compared to two conventional esterquat liposomal dispersions containing 5% active. The conventional esterquat actives were STEPANTEX VT-90, a tallow fatty acid-based TEA esterquat, and STEPANTEX ST-90, a tallow palm oil triglyceride-based TEA esterquat, both available from Stepan Company, Northfield, IL. The concentrated fabric softening compositions from Example 8 were used at 70% active without dilution, but each fabric softening composition (experimental and conventional) was dosed to provide a softener dosage of 0.15% weight on fabric (WOF), unless otherwise noted. The results of the softening study are shown in Table 3.

Table 3

[0062] The results in Table 3 show that the glycine betaine esterquats prepared from Guerbet alcohols having 24 to 28 total carbons can provide excellent softening properties. The C24 Guerbet alcohol glycine betaine/M10/PEG200 solvent system provided softening equal to ST-90, while the C24 Guerbet alcohol glycine betaine esterquat/DEP solvent provided better softening than ST-90. The C24 Guerbet alcohol glycine betaine esterquat/DEP solvent also provided softening equal to VT-90 when dosed at a slightly higher use level. The C28 Guerbet alcohol glycine betaine esterquat/DEP solvent provided softening equal to VT-90. These results demonstrate that a fabric softening composition having a BCI of 100 can provide softening performance at least equal to conventional esterquat fabric softeners. The results also show that the glycine betaine brassicyl esterquat and the glycine betaine esterquats prepared from Guerbet alcohols having 16 or 20 total carbons provided softening that was inferior to that of ST-90.

Example 10

[0063] A 10% active esterquat formulation was made using the esterquat from Example 6 using the low-active preparation method described above. Upon completion, a homogeneous dispersion was obtained.

[0064] The present technology is now described in such full, clear and concise terms as to enable a person skilled in the art to which it pertains, to practice the same. It is to be understood that the foregoing describes preferred embodiments of the present technology and that modifications may be made therein without departing from the spirit or scope of the present technology as set forth in the appended claims. Further, the examples are provided to not be exhaustive but illustrative of several embodiments that fall within the scope of the claims.