EP2872611B1 - Glycoldilevulinate als kopplungsmittel in reinigerformulierungen - Google Patents

Glycoldilevulinate als kopplungsmittel in reinigerformulierungen Download PDF

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Publication number
EP2872611B1
EP2872611B1 EP12780600.8A EP12780600A EP2872611B1 EP 2872611 B1 EP2872611 B1 EP 2872611B1 EP 12780600 A EP12780600 A EP 12780600A EP 2872611 B1 EP2872611 B1 EP 2872611B1
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weight
glycol
water
cleaning formulation
dilevulinate
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English (en)
French (fr)
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EP2872611A1 (de
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David C. Busby
Molly I-Chin Busby
William KRUPER, Jr.
Mark F. Sonnenschein
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons
    • C11D3/187—Hydrocarbons aromatic
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons
    • C11D3/188—Terpenes
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/24—Organic compounds containing halogen
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/266—Esters or carbonates
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5018—Halogenated solvents
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5022—Organic solvents containing oxygen
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5027—Hydrocarbons

Definitions

  • the present invention relates to cleaning formulations comprising water, one or more organic solvents having low solubility in water such as aliphatic hydrocarbons, aromatic hydrocarbons, or other organic compounds, and an alkylene glycol dilevulinate.
  • the alkylene glycol dilevulinates are excellent solvents for coupling the organic solvents with water.
  • Organic solvents are compounds that can be used to dissolve, soften, melt, or extract another compound, such as grease, soil, oil, paint, glue, stains, etc., and, therefore, are commonly used in cleaning formulations.
  • Typical organic solvents include aliphatic hydrocarbons, isoparaffins, aromatic hydrocarbons, chlorinated hydrocarbons, terpenes and d-limonene, among others.
  • Unfortunately, many organic solvents have limited solubility, or practically zero solubility, in water which severely limits the amounts that can be added to water-based cleaning formulations sometimes to the point where their beneficial effects cannot be realized.
  • Coupling agents are compounds that facilitate dissolution and dispersion of organic solvents, into water-based formulations, in greater amounts than otherwise possible, while the formulations retain their clarity, viscosity and homogeneity.
  • Various coupling agents are known for use in cleaning formulations including propylene glycol, diethylene glycol, glycol ethers, and surfactants, among others. See U.S. Patent Nos. 4,511,488 .
  • lower glycol ethers are volatile organic compounds (VOCs) which are environmentally undesirable.
  • VOCs volatile organic compounds
  • Some higher glycol ethers have lesser solubility in water-based systems, which limits their utility as coupling agents.
  • WO 2010/138907 discloses a solution comprises a solute dissolved in an aqueous cosolvent mixture, where the aqueous cosolvent is a mixture that includes water and at least one alkyl ketal ester that is miscible in water at the relative proportions of it present in the cosolvent mixture.
  • the preferred alkyl ketal esters are based upon levulinic acid. Esters of levulinic acid are well known and described in the art as plasticizers and solvents. For example, GB423919 describes the production of esters of levulinic acid with modified polyhydric alcohols which are useful as plasticizers for cellulose derivatives in coating applications.
  • U.S. Patent No. 2,654,723 describes the preparation of diethylene glycol dilevulinate by heating a mixture of levulinic acid and diethylene glycol, in a solvent such as toluene and in the presence of an acid catalyst.
  • WO 2010/102203 describes the preparation of alkyl levulinates by an acid-catalyzed reaction of furfuryl alcohol with other alcohols including methanol, ethanol, propanol, isopropanol, butanol, and isobutanol.
  • U.S. Patent No. 3,203,964 a process is described for manufacturing levulinic acid esters by heating furfuryl alcohol with another alcohol selected from the group consisting of unsubstituted primary and secondary carbon chain and oxygen-carbon chain aliphatic and carbon ring and oxygen-carbon ring cycloaliphatic alcohols containing from 1 to 10 carbon atoms, in the presence of a an acid catalyst.
  • U.S. Patent No. 3,203,964 states that the levulinic acid esters are useful as plasticizers or solvents.
  • GB478854 describes the use of lower alkylene glycol dilevulinates (e.g., dilevulinates of propylene glycol, diethylene glycol, ethylene glycol, trimethylene glycol (1,3-propanediol), 1,3-butylene glycol and dimethyl-dimethylol) as suitable high boiling softening agents for cellulosic pellicles.
  • U.S. Patent No. 2,581,008 discloses the preparation of dilevulinates of mono-, di- and tri-ethoxylated diols and their use as plasticizers for polyvinyl acetals and other polymers.
  • Furfuryl alcohol and levulinic acid are two of the reactants that can be used to manufacture esters of levulinic acid, e.g., alkylene glycol dilevulinates. They are both inexpensive renewable feedstocks available from biomass. Thus, the use of levulinates as solvents in water-based cleaning formulations would be economically and environmentally beneficial.
  • the present invention provides for the use of alkylene glycol dilevulinates as new alternative coupling agent solvents in water-based formulations.
  • the present invention provides a cleaning formulation comprising: (A) an aqueous solvent comprising water; (B) an active component comprising an organic solvent; and (C) a coupling agent comprising an alkylene glycol dilevulinate.
  • the alkylene glycol dilevulinate has the general formula, CH 3 C(O)CH 2 CH 2 C(O)O-R-O(O)CCH 2 CH 2 C(O)CH 3 , wherein R is a C 2 -C 8 straight chain or branched alkylene moiety, and the two levulinate groups (CH 3 C(O)CH 2 CH 2 C(O)O-) may be attached to adjacent, or non-adjacent, carbon atoms of the alkylene moiety.
  • R may be a C 2 -C 3 alkylene moiety
  • the alkylene glycol dilevulinate may be selected from the group consisting of: ethylene glycol dilevulinate, 1,2-propylene glycol dilevulinate and 1,3-propylene glycol dilevulinate.
  • the organic solvent may have a solubility of no more than 10%, or no more than 5%, by weight, in water at 25oC and atmospheric pressure, based on the total weight of the organic solvent and water in solution.
  • the organic solvent may be at least one compound selected from the group consisting of: an aliphatic hydrocarbon, an aromatic hydrocarbon, a chlorinated hydrocarbon, a terpene, lemon oil, pine oil, methyl soyate and d-limonene.
  • the aqueous solvent comprising water (A) may be present in an amount of from 90% to 98% by weight
  • the active component comprising an organic solvent (B) may be present in an amount of from 0.1% to 5.0% by weight
  • the coupling agent comprising an alkylene glycol dilevulinate (C) may be present in an amount of from 0.1% to 6.0%, all weight percentages based on the total weight of the cleaning formulation.
  • the present invention relates to the use of alkylene glycol dilevulinates or mixtures of alkylene glycol dilevulinates in water-based cleaning formulations to couple active components comprising organic compounds such as solvents or fragrances, having low or zero water solubility, with water.
  • Alkylene glycol dilevulinates can be economically produced from levulinic acid and a glycol.
  • Levulinic acid is available from biomass and is, therefore, a renewable environmentally-friendly resource.
  • glycols such as 1,2-propylene glycol and 1,3-propylene glycol are biorenewable and, therefore, also environmentally-friendly materials.
  • Alkylene glycol dilevulinates are high boiling, clear liquids with minimal odor and are not volatile organic compounds (VOCs). These particular characteristics provide benefits and advantages to their use as alternative coupling agents in water-based cleaning formulations. For example, traditional coupling agents such as propylene glycol, diethylene glycol and lower glycol ethers are volatile organic compounds (VOCs) which are environmentally undesirable. Also, with the exception of dipropylene glycol methyl ether, glycol ethers are not as effective couplers as the alkylene glycol dilevulinates. The alkylene glycol dilevulinates are partially to completely water soluble and are not VOCs.
  • VOCs volatile organic compounds
  • alkylene glycol dilevulinates are water soluble and, therefore, useful as coupling agents in water-based systems is a surprising and unexpected benefit. Furthermore, applicants have discovered that alkylene glycol dilevulinates provide better coupling performance which allows the use of greater amounts of organic solvents having low or zero water solubility with water, than when traditional coupling agents are used. Inclusion of greater amounts of the organic solvents increases cleaning efficiency while maintaining preferred formulation characteristics such as homogeneity, clarity, stability and viscosity.
  • alkylene glycol dilevulinates could be particularly useful in aerosol products such as hair care products, sanitizers, and insecticides, and spray applied consumer products.
  • These dilevulinate solvents allow the formulation of more efficient, safer and more environmentally friendly formulations and may facilitate the development of many novel formulations suitable for cleaning, coatings, pigment dispersants, pesticides, and agricultural applications.
  • an alkylene glycol dilevulinate and “alkylene glycol dilevulinates” are both meant to include the presence of one or more compounds having the general formula, CH 3 C(O)CH 2 CH 2 C(O)O-R-O(O)CCH 2 CH 2 C(O)CH 3 , wherein R is a C 2 -C 8 straight chain or branched alkylene moiety, and the two levulinate groups (CH 3 C(O)CH 2 CH 2 C(O)O-) may be attached to adjacent, or non-adjacent, carbon atoms of the alkylene moiety.
  • an "alkylene glycol dilevuninate” may be one compound which satisfies the foregoing general formula, or a mixture of such compounds. Where a mixture of alkylene glycol dilevulinates is synthesized or otherwise available, it is not necessary that the various species from one another before using the mixture in a cleaning formulation in accordance with the present invention.
  • organic active components is meant to include organic materials that perform a particular function in the cleaning formulations, such as organic solvents, fragrances, etc.
  • Organic solvents as the term is used herein, means compounds that dissolve, soften, melt, or extract another compound, such as grease, soil, oil, paint, glue, stains, etc., and which are, therefore, commonly used in cleaning formulations.
  • Typical organic solvents include, without limitation, aliphatic hydrocarbons, isoparaffins, aromatic hydrocarbons, chlorinated hydrocarbons, and terpenes, among others.
  • fragrances means organic compounds that impart a particular odor to the cleaning formulation, and may or may not also provide the same function as organic solvents.
  • Typical fragrances include, for example, d-limonene, lemon oil and pine oil.
  • Coupled agents means compounds that facilitate dissolution and dispersion of organic solvents, into water-based formulations, in greater amounts than otherwise possible, while the formulations retain their preferred characteristics of clarity, viscosity and homogeneity.
  • Traditional coupling agents used in cleaning formulations include, without limitation, propylene glycol, diethylene glycol, glycol ethers, and some surfactants, among others.
  • endpoints of ranges are considered to be definite and are recognized to incorporate within their tolerance other values within the knowledge of persons of ordinary skill in the art, including, but not limited to, those which are insignificantly different from the respective endpoint as related to this invention (in other words, endpoints are to be construed to incorporate values "about” or “close” or “near” to each respective endpoint).
  • the range and ratio limits, recited herein, are combinable. For example, if ranges of 1-20 and 5-15 are recited for a particular parameter, it is understood that ranges of 1-5, 1-15, 5-20, or 15-20 are also contemplated and encompassed thereby.
  • the cleaning formulations of the present invention comprise an aqueous solvent comprising water, an active component comprising at least one organic solvent, and at least one alkylene glycol dilevulinate.
  • the aqueous solvent may comprise up to 100% water.
  • cleaning formulation may comprise the aqueous solvent comprising water in an amount between 70 and 98% by weight, based on the total weight of the formulation.
  • the aqueous solvent comprising water may be present in an amount between 94 and 98% by weight.
  • the organic active component may be an organic solvent or fragrance and may have a solubility in water of not more than 10% by weight at 25oC and atmospheric pressure, or for example, not more than 5%, or even 1%, by weight at 25oC and atmospheric pressure, based on the total weight of the organic solvent or fragrance and water in solution.
  • Typical examples include, without limitation, d-limonene, lemon oil, pine oil, methyl soyate, and terpenes.
  • the cleaning formulations may comprise an organic active component in an amount between 0.1 to 20.0% by weight, based on the total weight of the formulation.
  • the organic active component may be present in an amount between 0.5 to 3.0% by weight.
  • alkylene glycol dilevulinates suitable for use in the present invention are lower alkylene glycol dilevulinates of general formula CH 3 C(O)CH 2 CH 2 C(O)O-R-O(O)CCH 2 CH 2 C(O)CH 3 , derived from alkylene glycols having the general formula HO-R-OH, wherein R is a C 2 -C 8 straight chain or branched alkylene moiety, and the two hydroxyl groups may be on adjacent carbons, for example ethylene glycol and 1,2-propylene glycol, or on non-adjacent carbons, for example 1,3-propanediol or 1,6-hexanediol.
  • Particularly suitable are alkylene glycol dilevulinates of the foregoing general formula, wherein R is a C 2 -C 3 alkylene, such as ethylene, 1,2-propylene, or 1,3-propylene.
  • Ethylene glycol dilevulinate is 100% water soluble while 1,2-propylene glycol dilevulinate (1,2-PGDL) is 10% soluble by weight in water, and 1,3-propylene glycol dilevulinate (1,3-PGDL) is 25% soluble. All three compounds also dissolve aromatic hydrocarbon compounds such as toluene and xylene, while having limited solubility for simple aliphatic hydrocarbons such as hexane and cyclohexane.
  • C 2 -C 3 alkylene glycol dilevulinates appear to provide the greatest benefits when used as coupling agents in water-based cleaning formulations.
  • the cleaning formulations may suitably comprise the alkylene glycol dilevulinate in an amount between 0.1 and 6.0% by weight, based on the total weight of the formulation.
  • the alkylene glycol dilevulinate may be present in the cleaning formulations in an amount between 0.5 and 3.0% by weight.
  • Processes for preparing esters of levulinates are well known and commercially practiced.
  • International Patent Application No. WO 2010/102203 describes reacting furfuryl alcohol with other alcohols (e.g., methanol, ethanol, propanol, isopropanol, butanol, and isobutanol), in equimolar amounts, in the presence of an acid catalyst, to produce corresponding alkyl levulinates.
  • Alkylene glycol dilevulinates suitable for use in accordance with the cleaning formulation of the present invention may be prepared by any process known now or in the future and is not particularly limited.
  • U.S. Patent No. 2,654,723 describes the preparation of diethylene glycol dilevulinate to involve mixing appropriate amounts of levulinic acid, diethylene glycol and toluene (as the reaction solvent), heating the mixture to react the levulinic acid and diethylene glycol and to remove water produced by that reaction, followed by removing the toluene by stripping to yield an amount of diethylene glycol dilevulinate, which has a boiling point above 200oC. From this source, it is seen that production of a dilevulinate from levulinic acid and an alkylene glycol requires providing these reactants at a molar ratio of (levulinic acid):(alkylene glycol) of at least 2:1.
  • glycol dilevulinates may be conveniently prepared, for instance, by the method described in the examples provided hereinbelow.
  • alkylene glycol dilevulinates suitable for use in the present invention include, without limitation, those prepared from any linear or branched C 2 -C 8 mono-, di-, or tri-alkylene glycol, and levulinic acid.
  • cleaning formulations in accordance with the present invention may contain ingredients in addition to water, an organic active component and a coupling agent.
  • the cleaning formulations may also comprise one or more surfactants, buffers, chelating agents, biocides, fragrances, viscosity modifiers, colorants, and polymers, among other things.
  • Suitable surfactants include, without limitation, sodium linear alkylbenzene sulfonates, alkyl sulfates, alpha olefin sulfonates, acyl sarcosinates, sodium salt of coconut fatty acids, sulfonated alkyl esters, alkyl polyglucosides, primary alcohol ethoxylates, alkyl polypentasides, secondary alcohol ethoxylates, EO-PO and EO-BO block polymers, and sodium 3-dodecylamino-propionate.
  • Suitable buffers include, for example, without limitation, sodium hydroxide (NaOH), alkanolamines, amines, ammonia, alkali metal carboxylates, citric acid, sodium citrate, and lactic acid.
  • Suitable chelating agents include, without limitation, ethylene diamine-N,N'-tetraacetic acid, the mono-, di-, tri-, and tetra sodium salts of (EDTA), nitriloacetic acid, trisodium salt (NTA), hydroxyl ethyl iminodiacetic acid, disodium salt (HEIDA), methyl glycinediacetic acid, trisodium salt (MGDA), glutamic acid, N,N-diacetic acid tetrasodium salt (GLDA), iminodiacetic acid, tetrasodium salt, (IDS), tri(hydroxymethyl)amino methane (TRIS), 2-amino-2-ethyl 1,3-propanediol, 2-amino-2-methyl propanol, 2-amino-2-methyl-1,3-propanediol, and polyamines.
  • EDTA ethylene diamine-N,N'-tetraacetic acid
  • Suitable colorants include, without limitation, dyes.
  • Polymers suitable for use in the cleaning formulations of the present invention include, without limitation, polyacrylate homopolymers and copolymers, METHOCELs, ETHOCELs, hydroxyethyl cellulose, POLYOXs, polyethylene glycols, polypropylene glycols, polyvinylpyrrolidones, and polyvinyl alcohols.
  • 1,3-propanediol dilevulinate and 1,2-propanediol dilevulinate were prepared in a similar manner with overall yields of 70% and 59% respectively.
  • Each formulation contained the following ingredients in the following amounts shown in the following TABLE OF STANDARD INGREDIENTS Examples 1-24: TABLE OF STANDARD INGREDIENTS - Examples 1-24 Name Amount (wt %) Description/Comment VERSENE HEIDA 1.00 Chelating agent, commercially available from the Dow Chemical Company of Midland, Michigan, U.S.A. An aqueous solution of disodium ethanoldiglycine which is readily biodegradable.
  • Diisopropanolamine (DiPA) 0.50 A buffer replaces traditional monoethanolamine (MEA) buffer Sodium Hydroxide (NaOH) 0.20 Buffer, pH adjuster Water variable Aqueous solvent Fragrance 0.50 one of the following as listed in TABLE 1 "outdoor” “orange” “lemon”
  • TABLE 1 presents the results of testing various formulations containing difficult-to-couple fragrances (organic active ingredients), i.e., "outdoor”, “orange” and “lemon,” using the aforesaid testing procedure.
  • the cleaning formulations were in either:
  • Figures 1-8 relate to the Set of Comparative Examples.
  • Each circle represents one sample formulation. More particularly, each of Figures 1 & 5 provide a schematic grid diagram of the general layout of sample formulations having various types of glycol ethers as coupling agents and various amounts of d-limonene fragrance, in the presence of 1% SLS surfactant and absence (0% SLS) of surfactant.
  • rows A & B of the grid in Figure 1 were formulations that each had 0.25% by weight d-limonene.
  • rows A & B of each of Figures 2-4 & 6-8 depict formulations that had 0.25% by weight d-limonene.
  • Columns 1 & 2 of the grid in Figure 1 were formulations that contained various amounts of BuCb , a glycol ether, as the coupling agent. More specifically, Column 1 of the grid in Figure 1 shows that for each vertical pair of formulations, the top formulation had 1% by weight BuCb and the bottom one had 10% by weight BuCb. Similarly, Column 2 of the grid in Figure 1 shows that for each vertical pair of formulations, the top formulation had 5% by weight BuCb and the bottom one had 20% by weight BuCb. This information can be similarly translated to Columns 1 & 2 of Figures 2-4 .
  • the sample formulation at Row D, Column 6 contained the standard ingredients listed in the TABLE above for Sets I & II, as well as 0.75% by weight d-limonene and 20% by weight HxCb as the coupling agent, based on the total weight of the formulation.
  • Figures 2-4 & 6-8 show the results (clear/white or cloudy/black) for the sample formulations identified in the grids of Figures 1 and 5 at 5°C, room temperature (25°C), and 40°C, respectively. Clear indicates successful coupling of the d-limonene and cloudy indicates poor or no coupling.
  • Figures 9-16 relate to the Set II of Working Examples. As with Figures 1-8 , each circle represents one sample formulation. More particularly, Figure 9 provides a schematic grid diagram of the general layout of sample formulations having various types of alkylene glycol dilevulinates as coupling agents and various amounts of d-limonene fragrance. For instance, rows A & B of the grid in Figure 9 were formulations that each had 0.25% by weight d-limonene. Thus, rows A & B of each of Figures 10-12 & 14-16 depict formulations that had 0.25% by weight d-limonene.
  • Columns 1 & 2 of the grid in Figure 9 were formulations that contained various amounts of 1,2-ethylene glycol dilevulinate (1,2-EGDL) as the coupling agent, in accordance with the present invention. More specifically, Column 1 of the grid in Figure 9 shows that for each vertical pair of formulations, the top formulation had 1% by weight 1,2-EGDL and the bottom one had 10% by weight 1,2-EGDL. Similarly, Column 2 of the grid in Figure 9 shows that for each vertical pair of formulations, the top formulation had 5% by weight 1,2-EGDL and the bottom one had 20% by weight 1,2-EGDL. This information can be similarly translated to Columns 1 & 2 of Figures 10-12 & 14-16 .
  • 1,2-ethylene glycol dilevulinate 1,2-ethylene glycol dilevulinate
  • the sample formulation at Row F, Column 6 contained the standard ingredients listed in the TABLE above for Sets I & II, as well as 1.5% by weight d-limonene and 20% by weight 1,2-EGDL as the coupling agent, based on the total weight of the formulation.
  • Figures 10-12 & 14-16 show the results (clear/white or cloudy/black) for the sample formulations identified in the grids of Figures 9 & 13 at 5°C, room temperature (25°C), and 40°C, respectively. Clear indicates successful coupling of the d-limonene and cloudy indicates poor or no coupling.
  • Figures 1-16 showed the phase stability data of glycol ethers and alkylene glycol dilevulinates with varying levels of d-limonene in the presence of 1% SLS surfactant and absence (0% SLS) of surfactant.
  • Each formulation contained the following ingredients in the following amounts shown in the following TABLE OF STANDARD INGREDIENTS Examples A-FF: TABLE OF STANDARD INGREDIENTS - Examples A-FF Name Amount (wt %) Description/Comment VERSENE HEIDA 0.5 Chelating agent, commercially available from the Dow Chemical Company of Midland, Michigan, U.S.A.
  • An aqueous solution of disodium ethanoldiglycine which is readily biodegradeable. It is particularly useful for chelation of iron in mildly alkaline solutions Diisopropanolamine (DiPA) 0.50 A buffer, replaces traditional monoethanolamine (MEA) buffer Sodium Hydroxide (NaOH) 0.20 Buffer, pH adjuster Water variable Aqueous solvent
  • Each formulation contained a total of either 0.5% or 1.0% surfactants, as follows and indicated in TABLE 2 below:
  • NEODOL 25-7 a C 12 -C 15 alcohol mixture containing an average of 7 moles of ethylene oxide per mole of alcohol.
  • NEODOL 45-7 a C 14 -C 15 alcohol mixture containing an average of 7 moles of ethylene oxide per mole of alcohol.
  • Hard surface cleaning power of the formulations was tested by the removal of soil from a vinyl tile. Vinyl tiles were cut to match the sample size of 11.5 cm x 7.5 cm and 500 ⁇ L of 3% Carbon Black Brazil soil was applied to the grooved side of the tile using a foam applicator. The tiles were set to dry for approximately 24 hours, and then the tile was placed in the SCiD plate and set on the orbital shaker. 400 ⁇ L of the cleaning solutions were dispensed into each well along with one carpeted scrubbie, and the samples were run on the shaker for five minutes. For each sample, 3 wells were tested, and the samples were run side by side with a good and bad cleaning standard. The samples were scanned into the computer and analyzed by the ImageJ software.
  • the cleaning power was measured by the average gray value of the well, and the cleaning power of the sample was measured by the average of the gray value of the three wells.
  • a higher gray value corresponds to a lighter circle and a higher cleaning power, while a lower gray value corresponds to a darker circle and a lower cleaning power.
  • TABLE 2 presents the results of testing various formulations containing different coupling agents and surfactant combinations, using the aforesaid testing procedure. It is noted that values for filming and streaking each run from 1 to 10, with the lowest numbers representing the least filming or streaking and, therefore, being the preferred values. For the "average grey" performance characteristic, the higher values are considered more preferable.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Fats And Perfumes (AREA)
  • Cosmetics (AREA)

Claims (10)

  1. Eine Reinigungsformulierung, die Folgendes beinhaltet:
    (A) ein wässriges Lösungsmittel, das Wasser beinhaltet;
    (B) eine aktive Komponente, die ein organisches Lösungsmittel beinhaltet; und
    (C) ein Kopplungsmittel, das ein Alkylenglycoldilevulinat mit der allgemeinen Formel CH3C(O)CH2CH2C(O)O-R-O(O)CCH2CH2C(O)CH3 beinhaltet, wobei R ein geradkettiger oder verzweigter C2-C8-Alkylenanteil ist und die zwei Levulinatgruppen (CH3C(O)CH2CH2C(O)O-) an angrenzende oder nicht angrenzende Kohlenstoffatome des Alkylenanteils gebunden sein können.
  2. Reinigungsformulierung gemäß Anspruch 1, wobei das organische Lösungsmittel in Wasser bei 25 °C und einem atmosphärischen Druck, bezogen auf das Gesamtgewicht des organischen Lösungsmittels und Wassers in der Lösung, eine Löslichkeit von nicht mehr als 10 Gew.-% aufweist.
  3. Reinigungsformulierung gemäß Anspruch 1, wobei das organische Lösungsmittel mindestens eine Verbindung ist, die aus der Gruppe ausgewählt ist, die aus Folgendem besteht: einem aliphatischen Kohlenwasserstoff, einem aromatischen Kohlenwasserstoff, einem chlorierten Kohlenwasserstoff, einem Terpen, Zitronenöl, Kiefernöl, Methylsoyat und d-Limonen.
  4. Reinigungsformulierung gemäß Anspruch 1, wobei R ein C2-C3-Alkylenanteil ist.
  5. Reinigungsformulierung gemäß Anspruch 4, wobei das Alkylenglycoldilevulinat eine oder mehrere Verbindungen ist, die aus der Gruppe ausgewählt ist/sind, die aus Folgendem besteht: Ethylenglycoldilevulinat, 1,2-Propylenglycoldilevulinat und 1,3-Propylenglycoldilevulinat.
  6. Reinigungsformulierung gemäß Anspruch 1, wobei das wässrige Lösungsmittel, das Wasser beinhaltet, (A), in einer Menge von 90 Gew.-% bis 98 Gew.-% vorhanden ist, wobei die aktive Komponente, die ein organisches Lösungsmittel beinhaltet, (B), in einer Menge von 0,1 Gew.-% bis 5,0 Gew.-% vorhanden ist, und wobei das Kopplungsmittel, das ein Alkylenglycoldilevulinat beinhaltet, (C), in einer Menge von 0,1 Gew.-% bis 6,0 Gew.-% vorhanden ist, wobei sich alle Gewichtsprozente auf das Gesamtgewicht der Reinigungsformulierung beziehen.
  7. Reinigungsformulierung gemäß Anspruch 6, wobei das wässrige Lösungsmittel, das Wasser beinhaltet, (A), in einer Menge von 94 Gew.-% bis 98 Gew.-% vorhanden ist.
  8. Reinigungsformulierung gemäß Anspruch 6, wobei die aktive Komponente, die ein organisches Lösungsmittel beinhaltet, (B), in einer Menge von 0,5 Gew.-% bis 3,0 Gew.-% vorhanden ist.
  9. Reinigungsformulierung gemäß Anspruch 6, wobei das Kopplungsmittel, das ein Alkylenglycoldilevulinat beinhaltet, (C), in einer Menge von 0,5 Gew.-% bis 3,0 Gew.-% vorhanden ist.
  10. Reinigungsformulierung gemäß Anspruch 1, die weiter eine oder mehrere der nachfolgenden zusätzlichen Komponenten beinhaltet:
    (D) Tenside;
    (E) Chelatbildner;
    (F) Puffer/Mittel zur Regulierung des pH-Werts;
    (G) Biozide;
    (H) Duftstoffe;
    (I) Viskositätsmodifizierungsmittel;
    (J) Farbstoffe; und
    (K) Polymere.
EP12780600.8A 2012-08-31 2012-10-11 Glycoldilevulinate als kopplungsmittel in reinigerformulierungen Active EP2872611B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13/600,549 US8586522B2 (en) 2011-09-02 2012-08-31 Glycol dilevulinates as coupling agents in cleaning formulations
PCT/US2012/059657 WO2014035445A1 (en) 2012-08-31 2012-10-11 Glycol dilevulinates as coupling agents in cleaning formulations

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EP2872611A1 EP2872611A1 (de) 2015-05-20
EP2872611B1 true EP2872611B1 (de) 2016-08-10

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CN110757878B (zh) * 2019-10-31 2021-09-28 济宁科力光电产业有限责任公司 一种伺服压力机的压力故障检测系统及方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB423919A (en) 1933-05-08 1935-02-11 Du Pont Improvements in or relating to the production of esters and compositions containing same
US2170827A (en) 1936-01-04 1939-08-29 Du Pont Cellulosic pellicles and methods for producing same
US2581008A (en) 1948-08-14 1952-01-01 Monsanto Chemicals Oxa-glycol dilevulinates
US2654723A (en) * 1950-11-01 1953-10-06 Gen Tire & Rubber Co Polyvinyl composition and method of making same
US3203964A (en) 1961-11-06 1965-08-31 Quaker Oats Co Preparation of levulinic acid esters from furfuryl alcohol
US4511488A (en) 1983-12-05 1985-04-16 Penetone Corporation D-Limonene based aqueous cleaning compositions
US5922665A (en) * 1997-05-28 1999-07-13 Minnesota Mining And Manufacturing Company Aqueous cleaning composition including a nonionic surfactant and a very slightly water-soluble organic solvent suitable for hydrophobic soil removal
US6090765A (en) * 1997-12-12 2000-07-18 Church & Dwight Co., Inc. Composition for cleaning hard surfaces
JP3904400B2 (ja) * 2000-03-24 2007-04-11 株式会社資生堂 頭髪洗浄料
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WO2007094922A2 (en) 2006-01-20 2007-08-23 Archer-Daniels-Midland Company Levulinic acid ester derivatives as reactive plasticizers and coalescent solvents
CN102405205A (zh) 2009-03-05 2012-04-04 赛格提斯公司 制备乙酰丙酸烷基酯的方法
BRPI1012056A2 (pt) * 2009-05-29 2016-05-17 Segetis Inc solução solvente, composição de limpeza e métodos
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WO2012067962A1 (en) * 2010-11-16 2012-05-24 Dow Global Technologies Llc Hard surface cleaners comprising low voc, low odor alkanolamines

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CN104685046A (zh) 2015-06-03
WO2014035445A1 (en) 2014-03-06
JP2015531811A (ja) 2015-11-05
JP6050496B2 (ja) 2016-12-21
CN104685046B (zh) 2018-05-22
BR112015003775A2 (pt) 2019-12-17
EP2872611A1 (de) 2015-05-20

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