Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
  • C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols

Definitions

• This invention relates to surfactant compositions comprising blends of alkoxylated alcohols and their use in detergents, hard surface cleaners, foam flotation agents, and emulsifiers.
• the concentrates typically include one or more nonionic surfactants because they are compatible with all other surfactant types (e.g. anionic, cationic and zwitterionic surfactants).
• nonionic surfactants resist precipitation with hard water and offer excellent oil grease cleaning benefits.
• Household and industrial applications that employ ultra-concentrates include laundry detergents, hard surface cleaners, automatic dishwasher detergents, rinse aids, emulsification packages (such as agricultural-emulsifiers), and flotation systems (for applications such as paper de-inking and ore flotation).
• diluted refers both to dissolution of solids and reduction of concentration of liquids.
• liquid laundry detergent may be diluted in a tub of water.
• a powdered or block laundry detergent that is dissolved in a tub of water also would be referred to as "diluted.”
• a common problem for concentrated formulas that contain surfactants is formation of gels when a solid or liquid surfactant is diluted with water.
• a formulation or concentrate consisting primarily of a 9-mole ethoxylate of nonylphenol (such as TergitolTM NP- 9) forms resilient, slow-dissolving gels when mixed with water.
• these slow-dissolving gels require extensive mixing which can interfere with convenience and effectiveness of end-use or diluted formulations.
• One way the industry expresses a tendency of a surfactant to cause gels is a "gel range."
• a typical gel range describes a percentage of samples that form gels, out of a number of samples, each having increasing surfactant concentration.
• a gel range of less than 20% indicates that less than two samples out of nine samples form gels; the nine samples having surfactant concentrations of 10 wt.%, 20 wt.%, 30 wt. %, 40wt.%, 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.%, and 90 wt.%, each weight percentage (wt%) being based upon combined weight of surfactant and de-ionized water.
• a sample forms a gel when it is non- pourable for at least five seconds at 23 "centigrade (°C) when its container is inverted 180° so the container's open spout or mouth faces down.
• a surfactant ideally has no gel range. In other words, it does not form gels when mixed with water.
• the tendency to form gels can be overcome by adding an anti-gelling agent such as a solvent or a polyglycol to the formulation.
• an anti-gelling agent such as a solvent or a polyglycol
• a simple formulation containing 20 wt% of a 9-mole ethoxylate of nonylphenol (TergitolTM NP-9) and 80 wt% propylene glycol (each wt% based on formulation weight) will not form gels upon dilution with water.
• the addition of anti-gelling agents tends to increase overall complexity and cost of the formulation, and therefore may be undesirable.
• a surfactant In addition to gel formation tendency, an important physical property consideration for use in selecting a surfactant is its tendency to undergo a viscosity increase as temperatures fall or decrease.
• Surfactant users typically select "pour point” or “pour point temperature” as a general indicator of handling characteristics of a pure surfactant under reduced temperatures. They consider pour point as that temperature below which a liquid surfactant will fail to pour from a container.
• alkoxylates of fatty alcohols containing greater than about eight carbons are alkoxylates.
• the alkoxylates are typically block or random polymers of ethoxy, propoxy, butoxy, or even larger alkoxy groups. These alkoxylates vary in alkyl group size, usually represented by "R", and in number of alkoxy groups in a polymer chain, also referred to as "degree of alkoxylation".
• R alkyl group size
• degree of alkoxylation The number and size of alkoxylate groups affects surfactant performance attributes including dispersibility and stability in various solutions, detergency, foam formation, and cleaning performance.
• the global chemical industry has expressed increasing interest in using renewable resources, such as plant or seed oils, to reduce dependence on petroleum and natural gas feedstocks.
• Seed oils contain fatty acids that may be converted to alcohols using known technology.
• the alcohols may be converted to alcohol alkoxylates by methods such as those discussed in "Nonionic Surfactants", Martin, J. Schick, Editor, 1967, Marcel Dekker, Inc., or United States Patent Application Publication (USPAP) 2005/017099 IAl.
• Fatty acid alcohols may also be alkoxylated using metal cyanide catalysts including (but not limited to) those described in United States Patent Number (USP) 6,429,342.
• Alcohols derived from natural feedstocks tend to have carbon chains that are more linear, and less branched, than alcohols derived from petroleum and natural gas products, which may be regarded as semi-linear or branched.
• alcohols when produced via hydrogenation of fatty acids, alcohols tend to be primary alcohols, having only one reactive group and an even number of carbon atoms in each chain or molecule.
• natural feedstock-derived alcohols produce surfactants that may behave somewhat differently than their petroleum and natural gas analogs. For example, alkoxylates with a generally linear structure tend to self-associate and form gels to a greater extent in water than those with a semi-linear or branched structure.
• surfactants based upon alkoxylated, natural oil- derived alcohols often do not function as drop in replacements for surfactants based upon alkoxylated alcohols derived from petroleum and natural gas feedstocks. As they are not drop in replacements, formulators must accommodate differences between surfactants based on natural oils and surfactants based upon petroleum or natural gas in preparing formulations for various uses.
• Relatively short-chain alkoxylates of linear alcohols derived from petroleum or natural gas typically do not form gels, and are often used in applications to avoid gel formation.
• R contains from 6 to 10 carbon atoms (C O-1O or C ⁇ -Cio)
• TritonTM XL-80N based on an alkoxylate of a Cs-Cio blend of alcohols, exhibits a narrow gel range (less than 20% of the range from 0% to 100% dilution) and is often used in hard-surface formulations that require rapid dissolution in the absence of gels.
• blends of two or more nonionic surfactants are used.
• blends of alkoxylates, especially Ci O _i 6 alcohol alkoxylates to give surfactants with specific properties (e.g. a certain pour point, a low or reduced gel range, and a desired detergency) when used in an ultra-concentrated formulas appear to be unknown.
• USP 3,983,078 teaches the use of mixtures of long-chain alkylene oxide surfactants and short-chain alkylene oxide co- surfactants.
• the mixtures have a hydrophilic-lipophilic balance (HLB) in a range of from about 10.8 to 12.0.
• HLB hydrophilic-lipophilic balance
• These surfactants blends are claimed as one part of complex formulations or blends that incorporate builders (sodium tripolyphosphate), hydrotropes (sodium toluene sulfonate), thickeners (sodium carboxymethyl cellulose), and other additives.
• Illustrative mixtures include 60-80 wt% of the "long chain” component" and 20-40 wt% of the "short-chain” component, the weight percentages being based upon mixture weight and totaling 100 wt%.
• Patent Cooperation Treaty Publication (WO) 94/10278 describes blends of surfactants based on a mixture of component A with component B in weight ratios ranging from 4: 1 to 10: 1 (80 wt% to 91 wt% component A).
• Component A is defined as R ⁇ (OC 3 H(On-(OC 2 H 4 )P- OH, in which R 1 is an alkyl residue with 6 to 10 carbon atoms, n is a number from 0.5 to 8, p is a number from 4 to 10.
• Component B is defined as R 2 -(OC 2 H 4 )q-OH, in which R 2 is an alkyl residue with 10 to 22 carbon atoms and q is a number from 4 to 10.
• the example teaches a blend of 85% of a C 8 alkoxylate with 15% of a C 12 - I4 ethoxylate.
• One aspect of this invention is a surfactant composition
• a surfactant composition comprising at least one nonionic surfactant represented by Formula (I)
• x is a real number within a range of from 0.5 to 3
• y is a real number within a range of from 2 to 10
• R is a mixture of seed-oil based linear alkyl moieties with an alkyl moiety distribution as follows wherein each wt% is based upon weight of all alkyl moieties present in the distribution and all wt% for each distribution total 100 wt%:
• the surfactant compositions of the present invention preferably combine detergency or cleaning performance typical of C 11 -C 16 branched or semi-branched alkyl alkoxylates derived from petroleum with gel ranges and, more preferably, pour points and, still more preferably, dissolution in water characteristics, typical of C ⁇ -Cio branched or semi-branched alkyl alkoxylates derived from petroleum.
• the surfactant compositions of the present invention exhibit at least one, preferably more than one, and still more preferably all of several physical or performance properties.
• the properties are: a) a gel range of less than 20% when mixed with water; b) a pour point of less than 10 0 C, c) detergency for laundry; d) dynamic surface wetting and textile wetting similar to Tergitol NP-9 Surfactant; e) biodegradability as defined by European Detergent Directive (OECD 301 test); f) desirable foam properties based on Ross-Miles Foam test (initial foam > 100 mm, 5 min foam ⁇ 50 mm); g) dissolution time in water of less than 2 minutes; h) wetting times of less than 50 seconds at a surfactant in water concentration of 0.05 wt %, based on total weight of surfactant and water and i) a critical micelle concentration less than 500 ppm.
• the surfactant compositions of this invention find utility in ultra-concentrates, especially those used in applications such as laundry, hard surface cleaning, emulsification, and foam flotation processes.
• the surfactant compositions of this invention may replace conventional, petroleum-derived nonylphenol ethoxylates, alcohol ethoxylates or alcohol alkoxylates in many applications including (but not limited to) laundry detergents, hard surface cleaning agents, paints, coatings, flotation processing, emulsification, general wetting, adjuvants for agricultural chemicals, textile cleaning, textile processing, pulp processing, paper processing, mining, polyurethane foam processing, personal care, and oil field recovery.
• surfactant compositions of this invention comprise alkoxylates having at least three different length alkyl groups, with a preferred subset including at least four different length alkyl groups.
• the surfactant compositions of this invention have improved detergency, dissolution and handling properties relative to surfactant compositions having the same number of carbon atoms in alkyl groups, but derived from petroleum or natural gas.
• the surfactant compositions of the present invention have particular utility in an ultra- concentrate formulation where they constitute from 2 wt% to 90 wt% of the formulation, based upon total formulation weight.
• the surfactant compositions of the present invention allow one to minimize, preferably eliminate, use of anti-gelling agents, such as solvents or polyglycols, in formulating such ultra-concentrates.
• the surfactant compositions of the present invention comprise at least one, preferably more than one, nonionic surfactant represented by Formula (I)
• each C 3 H 6 O moiety may also be called a poly(oxypropylene) or PO moiety and each C 2 H 4 O moiety may also be called a poly(oxyethylene) or EO moiety.
• x is a real number within a range of from 0.5 to 3 and y is a real number within a range of from 2 to 10.
• R represents a mixture of linear alkyl moieties, most preferably a mixture of linear alkyl moieties that are alkoxylates of seed oil-derived alcohols. Even more preferably, R has an alkyl moiety distribution in accord with ranges shown in Table I below.
• R can be a mixture of just three alkyl moieties, C 8 , C 10 and Ci 2 . Any one or more of C 6 , Ci 4 and Ci 6 alkyl moieties may, but need not be, present in surfactant compositions of the present invention. When present, the amounts of Ce, Cu and C 16 alkyl moieties may satisfy any of their respective ranges as shown in Table 1 as long as all weight percentages total 100 wt%.
• the surfactants of the present invention are preferably prepared in a sequential manner that includes propoxylation (adding PO or poly(oxypropylene)) moieties of an alcohol or mixture of alcohols to form a PO block followed by ethoxylation (adding EO or poly(oxyethylene)) moieties to form an EO block attached to the PO block, but spaced apart from R which represents alkyl moieties from the alcohol or mixture of alcohols.
• Formula (I) above includes variables "x” and "y” that, taken together, establish a degree of alkoxylation in an oligomer distribution.
• "x” and “y” represent average degrees of, respectively, propoxylation and ethoxylation.
• the degree of propoxylation or "x” preferably falls within a range of from 0.5 to less than 4, more preferably within a range of from 0.5 to 3, still more preferably within a range of from 2 to 3, and even more preferably within a range of from 2.5 to 3.
• the degree of ethoxylation or "y” preferably falls within a range of from 2 to 10, more preferably within a range of from 2 to 8, still more preferably within a range of from 4 to 8 and even more preferably within a range of from 6 to 8.
• a preferred subset of surfactant compositions of the present invention as represented by Formula (I) include x being within a range of from 2.5 to 3, y remaining within a range of from 2 to 10 and R has an alkyl moiety distribution as shown in Table 2 below. Table 2. Percentages of alkyl moieties
• the surfactant compositions as shown in Table 2 must include a mixture of at least four alkyl moieties, C 8 , C 10 , C 12 and Ci 4 .
• C 6 , and Ci 6 alkyl moieties may, but need not be, present in surfactant compositions of this preferred subset of the present invention.
• the amounts of C 6 and Ci 6 alkyl moieties may satisfy any of their respective ranges as shown in Table 1 as long as all weight percentages total 100 wt%.
• the surfactant has a final cloud point, measured as a 1 wt% aqueous solution, in accord with American Society for Testing and Materials (ASTM) D2024 of 46.3 0 C.
• a seed-oil derived Cs -10 alcohol with a hydroxyl number of approximately 386 (corresponding to a blend consisting of about 55% n-decanol and about 45% n-octanol) with 500 g of a seed-oil derived C 12-16 blend having a hydroxyl value of approximately 288 (corresponding to a blend consisting of about 70 % n-dodecanol, 25% n- tetradecanol and 5% n-hexadecanol) to provide a mixed alcohol stream.
• the propoxylated and ethoxylated surfactant has a final cloud point of 34.4 0 C and a structure (based on raw material feeds) of Cs- I6 O(PO) 2 s(EO)sH.
• the alcohol has a hydroxyl number of approximately 386 (corresponding to a blend consisting of about 55% n-decanol and about 45% n-octanol).
• the changes include distillation for 30 minutes at 5 mm Hg rather than 45 minutes at 50 mm Hg as in Comp Ex A to attain a water content of less than 200 ppm.
• the changes also include 1050 g of PO, 1590 g of EO, addition of EO before propoxylation proceeds to a point where residual or unreacted PO reaches a level of less than 50 ppm and an increase in amount of acetic acid to 2.7 g.
• the propoxylated and ethoxylated surfactant has a final cloud point of 51.2 0 C and a structure (based on raw material feeds) of Cs- I0 O(PO) 2 s(EO) 6 5H.
• the propoxylated and ethoxylated surfactant has a final cloud point of 54.5°C and a structure (based on raw material feeds) of Ci 2 -i 4 ⁇ (PO) 2 s(EO)sH.
• Comp Ex E A 50:50 blend of Comp Ex A (C 8-10 O(PO) 3 (EO) 5 5 H ) and Comp Ex B (C 12- C 14 O(PO) 2 (EO) 7 H)
• Draves Wetting Test American Association of Textile Chemists and Colorists (AATCC) Test 17 (ASTM D2281) - Prepare 0.05 wt%, 0.10 wt% and 0.15 wt% solutions of surfactant in deionized water. Place a cotton skein (40/2 combed peeler yarn from Testfabrics, Inc.) in each solution and measure elapsed time until the skein collapses. In addition, calculate a concentration of surfactant required for wetting in 20 seconds based on a linear regression of a log time versus log concentration plot built on data from the 0.05 wt%, 0.10 wt% and 0.15 wt% solution testing Ross-Miles Foam Height Test -ASTM Dl 173
• CMC Surface Tension and Critical Micelle Concentration
• Dissolution Time Test Measure time required for 50 g of a surfactant to dissolve in one liter (L) of water at 20 0 C with stirring using an overhead stirrer operating at a stirring rate of 500 revolutions per minute (rpm).
• deionized water has a surface tension of 73 dynes / cm.
• the data in Table 3 demonstrate that order of alkoxylation is important, at least in terms of Draves Wetting Times for a 0.05 wt% concentration of surfactant, CMC and Ross Miles Foam Height Testing results as shown by comparing Comp Ex A (propoxylation followed by ethoxylation) and Comp Ex H (ethoxylation followed by propoxylation).
• the data in Table 3 also demonstrate that seed-oil based surfactants of the present invention perform well in Draves and Ross Miles Foam testing and have a desirable CMC. As shown in Table 4 below, such surfactants also have a low Gel Range.

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